CN107253935A - Trap compound, the preparation method of polymerizable compound and the method for using the manufacture raw material of hydrazine compound as polymerizable compound - Google Patents

Trap compound, the preparation method of polymerizable compound and the method for using the manufacture raw material of hydrazine compound as polymerizable compound Download PDF

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CN107253935A
CN107253935A CN201710233080.9A CN201710233080A CN107253935A CN 107253935 A CN107253935 A CN 107253935A CN 201710233080 A CN201710233080 A CN 201710233080A CN 107253935 A CN107253935 A CN 107253935A
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compound
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nmr
substituent
synthesis
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CN107253935B (en
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坂本圭
桐木智史
奥山久美
平加奈子
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Zeon Corp
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Nippon Zeon Co Ltd
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Abstract

The present invention is trap compound, the preparation method of polymerizable compound and the method for using the manufacture raw material of hydrazine compound as polymerizable compound.According to the present invention, it is possible to provide can obtain with practical low melting point, it is excellent relative to the dissolubility of general solvent, can the low cost manufacture method of the polymerizable compound of the polymerizable compound of optical film that be prepared and uniform polarised light conversion can be carried out in wide wave-length coverage and as useful trap compound of its preparing raw material etc..A kind of hydrazine compound, is any one in following formulas (E), (M), (Q), (S), (Y), (Z), (E1), (G1), (L1), (O1), (P1), (Y1), (Z1), (A2), (B2), (C2), (D2), (E2), (F2), (I2), (J2), (R2), (S2) and (T2).

Description

Trap compound, the preparation method of polymerizable compound and it regard hydrazine compound as polymerization The method that the manufacture raw material of property compound is used
The application is the divisional application of the application for a patent for invention of Chinese Application No. 201380046851.3, original bill application Entitled " polymerizable compound, polymerizable composition, polymerizable composition, macromolecule, the system of optically anisotropic body and polymerizable compound Preparation Method ", the applying date is on May 30th, 2013.
Technical field
The optical film of uniform polarised light conversion can be carried out in wide wave-length coverage the present invention relates to a kind of prepare Polymerizable compound, polymerizable composition, polymerizable composition and macromolecule, optically anisotropic body, and be used as the preparation of polymerizable compound The useful carbonyls of raw material, using the preparation method of the polymerizable compound of the carbonyls, and uses the carbonylation Compound as the preparing raw material of polymerizable compound method.
Background technology
Because panel display apparatus (FPD) by using optical films such as Polarizer or polarizers can carry out high-resolution It has been shown that, therefore it is widely used as the excellent display device by representative of television set.
Polarizer has is converted to 1/4 wavelength plate of circularly polarized light, the polarised light by rectilinearly polarized light by rectilinearly polarized light Vibration plane changes 90 degree 1/2 wavelength plate etc..These polarizers can be correctly with light ripple for certain specific monochromatic light 1/4 long λ or 1/2 λ phase difference are changed.
But, current polarizer, which has, is converted to the polarised light exported by polarizer asking for coloured polarised light Topic.The reason is that constitute the material of polarizer has wavelength dispersibility for phase difference, to the light as visible region The white light for the composite wave being mixed, produces the distribution in the polarized light state of each wavelength, so can not be in whole wavelength In the range of be adjusted to correct 1/4 λ or 1/2 λ phase difference.
The problem of in order to solve such, have studied various can provide the light of wide wave-length coverage the width of uniform phase difference Band phase difference plate, the polarizer (such as patent document 1~6) with so-called anti-wavelength dispersibility.
On the other hand, the high performance with the portable type information terminal such as portable personal, portable phone and popularization, It is required that strongly that the thickness of panel display apparatus is thinning.Thus, also require that as constituent part polarizer it is thin layer.
As thin layer method, combined by being coated with the polymerism containing low molecule polymerizable compound on film base material Thing is considered as most efficient method in recent years so as to the method for preparing polarizer.Carry out substantial amounts of with excellent wavelength The low molecule polymerizable compound of dispersivity or the exploitation (such as patent document 7~24) using its polymerizable composition, polymerizable composition.
But, it is not suitable for because the low molecule polymerizable compound or polymerizable composition, polymerizable composition described in these documents have The high-melting-point of processing in industrial process, so the problem of aspect of performance has following a large amount of：It is difficult to be coated on film, or it is aobvious Show that the temperature range of liquid crystal liquid crystal property is extremely narrow, or the solubility in industrial processes in usually used solvent is low, or they are gathered Anti- wavelength dispersibility deficiency of polymeric membrane obtained from conjunction etc..Further, since these low molecule polymerizable compounds etc. are used Using the synthetic method of very expensive reagent, synthesized by multiple steps, so also having problem in terms of cost.
Prior art document
Patent document
Patent document 1：Japanese Unexamined Patent Publication 10-68816 publications
Patent document 2：Japanese Unexamined Patent Publication 10-90521 publications
Patent document 3：Japanese Unexamined Patent Publication 11-52131 publications
Patent document 4：Japanese Unexamined Patent Publication 2000-284126 publications (US20020159005A1)
Patent document 5：Japanese Unexamined Patent Publication 2001-4837 publications
Patent document 6：International Publication No. 2000/026705
Patent document 7：Japanese Unexamined Patent Publication 2002-267838 publications
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Patent document 24：U.S. Patent No. 5,567,349.
The content of the invention
Invent problem to be solved
The present invention in view of above-mentioned current technology and implement, its object is to provide：It can obtain with practical low melting point, phase For general solvent dissolubility it is excellent, can low cost prepared, reflecting brightness it is low and can be in wide wave-length coverage Polymerizable compound, polymerizable composition, polymerizable composition and the macromolecule of the interior optical film for carrying out uniform polarised light conversion, optics is respectively to different Property body；And as the useful carbonyls of the preparing raw material of the polymerizable compound, use the polymerization of the carbonyls The preparation method of property compound, and the carbonyls is used as the method for the preparing raw material of polymerizable compound.
The means to solve the problem
The present inventor is furtherd investigate to solve above-mentioned problem.It was accordingly found that by using will be with following formula (I) The polymerizable compound of expression or containing above-mentioned polymerizable compound and polymerization initiator polymerizable composition, polymerizable composition polymerization and obtain Macromolecule as constituent material optically anisotropic body, can low cost prepare can be carried out in wide wave-length coverage it is equal The optical film of even polarised light conversion, so as to complete the present invention.
So, according to the present invention, it is possible to provide the polymerizable compound of (1)~(7), (8), the polymerizable composition, polymerizable composition of (9), (10), the macromolecule of (11), the optically anisotropic body of (12), the carbonyls of (13)~(16), the polymerism of (17) The preparation method of compound, and the above-mentioned carbonyls of (18) is used as the method for the preparing raw material of polymerizable compound.
(1) a kind of polymerizable compound, the polymerizable compound is represented with following formula (I).
[changing 1]
[in formula, Y1~Y8Independently of one another represent chemical single bond ,-O- ,-S- ,-O-C (=O)-,-C (=O)-O- ,-O- C (=O)-O- ,-NR1- C (=O)-,-C (=O)-NR1- ,-O-C (=O)-NR1-、-NR1- C (=O)-O- ,-NR1- C (=O)- NR1-、-O-NR1- or-NR1-O-.Herein, R1Expression hydrogen atom or the alkyl that carbon number is 1~6.
G1、G2Represent there can be the divalence chain linear aliphatic base that the carbon number of substituent is 1~20 independently of one another.In addition, In above-mentioned chain linear aliphatic base can be inserted into have-O- ,-S- ,-O-C (=O)-,-C (=O)-O- ,-O-C (=O)-O- ,-NR2-C (=O)-,-C (=O)-NR2-、-NR2- or-C (=O)-.But ,-the O- or-S- for excluding more than 2 are each adjacent to insertion Situation.Herein, R2Expression hydrogen atom or the alkyl that carbon number is 1~6.
Z1、Z2The alkenyl that the carbon number that can be replaced with halogen atom is 2~10 is represented independently of one another.
AxRepresent the carbon number with least one aromatic ring selected from aromatics hydrocarbon ring and aromatic heterocycle for 2~30 it is organic Base.
AyRepresent hydrogen atom, can have substituent carbon number for 1~20 alkyl, can have substituent carbon atom Alkenyl that number is 2~20, the carbon number that can have alkynyl that the carbon number of substituent be 2~20, can have a substituent be 3 ~12 cycloalkyl ,-C (=O)-R3、-SO2-R4,-C (=S) NH-R9Or with selected from aromatics hydrocarbon ring and aromatic heterocycle at least The carbon number of one aromatic ring is 2~30 organic group.Herein, R3Represent there can be the carbon number of substituent to be 1~20 Alkyl, the alkenyl that can be 2~20 with the carbon number of substituent can have the cycloalkanes that the carbon number of substituent be 3~12 Base, carbon number are 5~12 aromatic hydrocarbyl, R4Represent the alkene that alkyl, carbon number that carbon number is 1~20 are 2~20 Base, phenyl or 4- aminomethyl phenyls, R9Expression can have the alkyl that the carbon number of substituent is 1~20, can have substituent Alkenyl that carbon number is 2~20, the carbon that can have cycloalkyl that the carbon number of substituent be 3~12, can have substituent Atomicity is 5~20 aromatic group.Above-mentioned AxAnd AyThe aromatic ring being had can have substituent.In addition, above-mentioned AxWith AyIt can combine Ring is formed together.
A1Represent there can be the trivalent aromatic group of substituent.
A2、A3Represent there can be the divalence alicyclic type hydrocarbon that the carbon number of substituent is 3~30 independently of one another,
A4、A5Represent there can be the divalent aromatic radical that the carbon number of substituent is 6~30 independently of one another.
Q1Represent hydrogen atom or there can be the alkyl that the carbon number of substituent is 1~6.]
(2) polymerizable compound described in (1), wherein, above-mentioned AxAnd AyThe sum of contained pi-electron is more than 4 And less than 24.
(3) polymerizable compound described in (1) or (2), wherein, above-mentioned A1For that can have the trivalent phenyl ring base of substituent Or trivalent naphthalene nucleus base.
(4) polymerizable compound described in any one of (1)~(3), wherein, above-mentioned Y1~Y8Being each independently Learn singly-bound ,-O- ,-O-C (=O)-,-C (=O)-O- or-O-C (=O)-O-.
(5) polymerizable compound described in any one of (1)~(4), wherein, above-mentioned Z1、Z2It is each independently CH2 =CH-, CH2=C (CH3)-or CH2=C (Cl)-.
(6) polymerizable compound described in any one of (1)~(5), wherein, above-mentioned G1、G2Being each independently to have The carbon number of substituted base for 1~20 divalent aliphatic base [in the aliphatic group can be inserted into have-O- ,-O-C (=O)-,-C (=O)-O- or-C (=O)-.But ,-the O- for excluding more than 2 is adjacent to situation about inserting.].
(7) polymerizable compound described in any one of (1)~(6), wherein, above-mentioned G1、G2It is each independently carbon former Subnumber is 1~12 alkylidene.
(8) a kind of polymerizable composition, polymerizable composition, the polymerizable composition, polymerizable composition contains described in any one of above-mentioned (1)~(7) It is at least one kind of in polymerizable compound.
(9) a kind of polymerizable composition, polymerizable composition, the polymerizable composition, polymerizable composition, which contains in polymerization initiator and above-mentioned (1)~(7), appoints It is at least one kind of in polymerizable compound described in one.
(10) a kind of macromolecule, the macromolecule is by the polymerizable compound described in any one of above-mentioned (1)~(7) Or macromolecule obtained from the polymerizable composition, polymerizable composition polymerization described in (8) or (9).
(11) macromolecule described in (10), the macromolecule is liquid crystal liquid crystal property macromolecule.
(12) a kind of optically anisotropic body, macromolecule described in the optically anisotropic body using above-mentioned (11) as Constituent material.
(13) a kind of carbonyls, the carbonyls is represented with following formula (4)：
[changing 2]
In formula, Y1~Y8Independently of one another represent chemical single bond ,-O- ,-S- ,-O-C (=O)-,-C (=O)-O- ,-O- C (=O)-O- ,-NR1- C (=O)-,-C (=O)-NR1- ,-O-C (=O)-NR1-、-NR1- C (=O)-O- ,-NR1- C (=O)- NR1-、-O-NR1- or-NR1-O-.Herein, R1Expression hydrogen atom or the alkyl that carbon number is 1~6.
G1、G2Independently of one another represent can have substituent carbon number for 1~20 divalence chain linear aliphatic base [at this In chain linear aliphatic base can be inserted into have-O- ,-S- ,-O-C (=O)-,-C (=O)-O- ,-O-C (=O)-O- ,-NR2- C (=O)-,- C (=O)-NR2-、-NR2- or-C (=O)-.But ,-the O- or-S- for excluding more than 2 are each adjacent to situation about inserting.This Place, R2Expression hydrogen atom or the alkyl that carbon number is 1~6.].
Z1、Z2The alkenyl that carbon number that is unsubstituted or being replaced with halogen atom is 2~10 is represented independently of one another.
A1Represent there can be the trivalent aromatic group of substituent.
A2、A3Represent there can be the divalence alicyclic type hydrocarbon that the carbon number of substituent is 3~30 independently of one another.
A4、A5Represent there can be the divalent aromatic radical that the carbon number of substituent is 6~30 independently of one another.
Q1Represent hydrogen atom or there can be the alkyl that the carbon number of substituent is 1~6.}
(14) carbonyls described in (13), wherein, above-mentioned A1For that can have the trivalent phenyl ring base or three of substituent Valency naphthalene nucleus base.
(15) carbonyls described in (13) or (14), wherein, above-mentioned A2、A3Substitution can be had by being each independently The cyclohexyl radicals of base.
(16) carbonyls described in any one of (13)~(15), wherein, above-mentioned Z1、Z2It is each independently CH2 =CH-, CH2=C (CH3)-or CH2=C (Cl)-.
(17) a kind of preparation method of polymerizable compound, it is characterised in that make described in any one of (13)~(16) Carbonyls reacted with the hydrazine compound that is represented with following formula：
[changing 3]
(in formula, AxRepresent the carbon number with least one aromatic ring selected from aromatics hydrocarbon ring and aromatic heterocycle for 2~ 30 organic group.
AyRepresent hydrogen atom, can have substituent carbon number for 1~20 alkyl, can have substituent carbon atom Alkenyl that number is 2~20, the carbon number that can have alkynyl that the carbon number of substituent be 1~20, can have a substituent be 3 ~12 cycloalkyl ,-C (=O)-R3、-SO2-R4,-C (=S) NH-R9Or with selected from aromatics hydrocarbon ring and aromatic heterocycle at least The carbon number of one aromatic ring is 2~30 organic group.Herein, R3Represent there can be the carbon number of substituent to be 1~20 Alkyl, the alkenyl that can be 2~20 with the carbon number of substituent can have the cycloalkanes that the carbon number of substituent be 3~12 Base, carbon number are 5~12 aromatic hydrocarbyl, R4Represent the alkene that alkyl, carbon number that carbon number is 1~20 are 2~20 Base, phenyl or 4- aminomethyl phenyls, R9Expression can have the alkyl that the carbon number of substituent is 1~20, can have substituent Alkenyl that carbon number is 2~20, the carbon that can have cycloalkyl that the carbon number of substituent be 3~12, can have substituent Atomicity is 5~20 aromatic group.
Above-mentioned AxAnd AyThe aromatic ring being had can have substituent.
In addition, above-mentioned AxWith AyIt may then bond together to form ring.)
Wherein, the polymerizable compound is represented with following formula (I)：
[changing 4]
(in formula, Ax、Ay、Y1~Y8、Z1、Z2、G1、G2、A1~A5And Q1Represent implication same as described above.).
(18) carbonyls described in any one of (13)~(16) is used as the polymerization represented with following formula (I) The method of the preparing raw material of property compound：
[changing 5]
(in formula, Ax、Ay、Y1~Y8、Z1、Z2、G1、G2、A1~A5And Q1Represent implication same as described above.).
The effect of invention
According to polymerizable compound, polymerizable composition, polymerizable composition and the macromolecule of the present invention, it can obtain with practical low melting point, Dissolubility relative to general solvent is excellent, inexpensive can be prepared, reflecting brightness is low, and can be in wide wavelength model Enclose the interior optical film for carrying out uniform polarised light conversion.
Due to the present invention optically anisotropic body using the present invention macromolecule be used as constituent material, it is possible to low cost Prepared, reflecting brightness is low, and uniform polarised light conversion can be carried out in wide wave-length coverage.
Antireflection film can be prepared by the way that the membranaceous optically anisotropic body of the present invention is combined with Polarizer.The antireflection Film industrially can for example be suitable for the antireflection of touch panel, organic electroluminescent device.
The carbonyls of the present invention as the polymerizable compound of the present invention to prepare intermediate useful.
According to the preparation method of the polymerizable compound of the present invention, the polymerizable compound of the present invention can be effectively prepared.
By using the carbonyls of the present invention as preparing raw material, the poly- of the present invention can in high yield and be easily prepared Conjunction property compound.
Embodiment
The present invention is divided into 1) polymerizable compound, 2) polymerizable composition, polymerizable composition, 3) macromolecule, 4) optical anisotropy below The side of the preparation method of body, 5) carbonyls and 6) polymerizable compound and preparing raw material as polymerizable compound Method, is described in detail.It should be noted that, in the present invention, " can have substituent " is " unsubstituted or with substituent " Implication.
1) polymerizable compound
The polymerizable compound of the present invention is the compound represented with above-mentioned formula (I).
In formula, Y1~Y8Independently of one another represent chemical single bond ,-O- ,-S- ,-O-C (=O)-,-C (=O)-O- ,-O-C (=O)-O- ,-NR1- C (=O)-,-C (=O)-NR1- ,-O-C (=O)-NR1-、-NR1- C (=O)-O- ,-NR1- C (=O)- NR1-、-O-NR1- or-NR1-O-。
Herein, R1Expression hydrogen atom or the alkyl that carbon number is 1~6.
It is used as R1Carbon number be 1~6 alkyl, can include methyl, ethyl, n-propyl, isopropyl, normal-butyl, Sec-butyl, the tert-butyl group, n-pentyl, n-hexyl etc..
It is used as R1, preferably hydrogen atom or carbon number is 1~4 alkyl.
In the polymerizable compound of the present invention, preferably Y1~Y8Be each independently chemical single bond ,-O- ,-O-C (= O)-,-C (=O)-O- or-O-C (=O)-O-.
G1、G2Represent there can be the divalent aliphatic base that the carbon number of substituent is 1~20 independently of one another.
As the divalent aliphatic base that carbon number is 1~20, alkylidene, carbon that carbon number is 1~20 can be included former Subnumber is the divalent aliphatic base that 2~20 alkenylene etc. has chain structure, and carbon number is 3~20 cycloalkanes diyl (cycloalkanediyl) cyclenes diyl (cycloalkenediyl) that, carbon number is 4~20, carbon number are 10~30 The divalent aliphatic base such as divalence ester ring type condensed ring radical etc..
It is used as G1、G2Divalent aliphatic base substituent, the halogen such as fluorine atom, chlorine atom, bromine atoms, iodine atom can be included Plain atom, methoxyl group, ethyoxyl, positive propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, n-pentyloxy, just The carbon numbers such as hexyloxy are 1~6 alkoxy etc..Wherein, preferably fluorine atom, methoxyl group, ethyoxyl.
In addition, in above-mentioned aliphatic group can be inserted into have-O- ,-S- ,-O-C (=O)-,-C (=O)-O- ,-O-C (=O)- O-、-NR2- C (=O)-,-C (=O)-NR2-、-NR2- or-C (=O)-.But ,-the O- or-S- for excluding more than 2 each adjoin Situation about inserting adjacently.Herein, R2With above-mentioned R1Hydrogen atom or the alkyl that carbon number is 1~6, preferably hydrogen are represented in the same manner Atom or methyl.
As the group being inserted in above-mentioned aliphatic group, preferably-O- ,-O-C (=O)-,-C (=O)-O- ,-C (=O)-.
As the instantiation of the aliphatic group inserted with these groups ,-CH can be included2-CH2-O-CH2-CH2-、-CH2- CH2-S-CH2-CH2-、-CH2-CH2- O-C (=O)-CH2-CH2-、-CH2-CH2- C (=O)-O-CH2-CH2-、-CH2-CH2-C (=O)-O-CH2-、-CH2- O-C (=O)-O-CH2-CH2-、-CH2-CH2-NR2- C (=O)-CH2-CH2-、-CH2-CH2- C (= O)-NR2-CH2-、-CH2-NR2-CH2-CH2-、-CH2- C (=O)-CH2- etc..
Wherein, from the viewpoint of the effect desired by the present invention is showed better, G1、G2Preferred carbon independently of one another Alkenylene that alkylidene that atomicity is 1~20, carbon number are 2~20 etc. has the divalent aliphatic base of chain structure, more excellent Select methylene, ethylidene, trimethylene, propylidene, tetramethylene, pentamethylene, hexa-methylene, eight methylene, decamethylene [-(CH2)10-] etc. carbon number be 1~12 alkylidene, particularly preferred tetramethylene [- (CH2)4-], hexa-methylene [- (CH2)6-], eight methylene [- (CH2)8-] and decamethylene [- (CH2)10-]。
Z1、Z2The alkenyl that carbon number that is unsubstituted or being replaced with halogen atom is 2~10 is represented independently of one another.
It is used as the carbon number of the alkenyl, preferably 2~6.It is used as Z1And Z2Alkenyl substituent halogen atom, can arrange Enumerate fluorine atom, chlorine atom, bromine atoms etc., preferably chlorine atom.
It is used as Z1And Z2Carbon number for 2~10 alkenyl instantiation, CH can be included2=CH-, CH2=C (CH3)-、CH2=CH-CH2-、CH3- CH=CH-, CH2=CH-CH2-CH2-、CH2=C (CH3)-CH2-CH2-、(CH3)2C= CH-CH2-、(CH3)2C=CH-CH2-CH2-、CH2=C (Cl)-, CH2=C (CH3)-CH2-、CH3- CH=CH-CH2- etc..
Wherein, from the viewpoint of the effect desired by the present invention is showed better, it is used as Z1And Z2, independently of one another Preferably CH2=CH-, CH2=C (CH3)-、CH2=C (Cl)-, CH2=CH-CH2-、CH2=C (CH3)-CH2- or CH2=C (CH3)-CH2-CH2-, more preferably CH2=CH-, CH2=C (CH3)-or CH2=C (Cl)-, particularly preferably CH2=CH-.
AxRepresent the carbon number with least one aromatic ring selected from aromatics hydrocarbon ring and aromatic heterocycle for 2~30 it is organic Base.
In the present invention, " aromatic ring " refers to the cyclic structure of the armaticity with the broad sense for meeting Huckel rules, that is, has The cyclic conjugated structure of (4n+2) individual pi-electron, and the miscellaneous original such as wherein sulphur, oxygen, nitrogen representated by thiophene, furans, benzothiazole etc. The lone electron pair of son participates in pi-electron system and shows the structure of armaticity.
AxThe carbon number with least one aromatic ring selected from aromatics hydrocarbon ring and aromatic heterocycle be 2~30 organic group There can be multiple aromatic rings, can also have aromatics hydrocarbon ring and aromatic heterocycle.
As above-mentioned aromatics hydrocarbon ring, phenyl ring, naphthalene nucleus, anthracene nucleus etc. can be included.As above-mentioned aromatic heterocycle, pyrrole can be included Cough up ring, furan nucleus, thiphene ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, pyrazole ring, imidazole ring, oxazole rings, thiazole ring etc. Monocyclic aromatic heterocycle, benzothiazole ring, benzoxazole ring, quinoline ring, phthalazines ring, benzimidazole ring, benzopyrazoles ring, benzo Furan nucleus, benzothiophene ring, thiazolopyridin Huan, oxazoles and pyridine ring, thiazole and pyrazine Huan, oxazoles and pyrazine ring, thiazole are simultaneously Aromatic heterocycle of condensed ring such as pyridazine Huan, oxazoles and pyridazine ring, thiazole and pyrimidine ring, oxazoles and pyrimidine ring etc..
AxThe aromatic ring being had can have substituent.As such substituent, the halogen such as fluorine atom, chlorine atom can be included Plain atom, cyano group, the carbon number such as methyl, ethyl, propyl group is 1~6 alkyl, the carbon number such as vinyl, pi-allyl is 2~ 6 alkenyl, the carbon number such as trifluoromethyl is 1~6 haloalkyl, the substituted-amino, methoxyl group, ethoxy such as dimethylamino The carbon numbers such as base, isopropoxy are 1~6 alkoxy, nitro, the aryl ,-C (=O)-R such as phenyl, naphthyl5,-C (=O)- OR5,-SO2R6Deng.Herein, R5Represent alkenyl or carbon number that alkyl, carbon number that carbon number is 1~20 are 2~20 For 3~12 cycloalkyl, R6With following R4The alkene that alkyl, carbon number that carbon number is 1~20 are 2~20 is represented in the same manner Base, phenyl or 4- aminomethyl phenyls.
In addition, AxThe aromatic ring being had can have multiple identical or different substituents, two substituents mutually adjoined Also it is bonding to form ring together.The ring of formation can be monocyclic or fused polycycle, or unsaturation ring or saturated rings.
It should be noted that, AxCarbon number for " carbon number " of 2~30 organic group to refer to carbon without substituent former Overall total carbon atom number (the following A of the organic group of sonyIt is same.).
It is used as AxThere is the carbon number of at least one aromatic ring selected from aromatics hydrocarbon ring and aromatic heterocycle to have for 2~30 Machine base, can include aromatic hydrocarbon ring group, aromatic heterocyclic radical, with least one virtue selected from aromatic hydrocarbon ring group and aromatic heterocyclic radical The carbon number of ring is 3~30 alkyl, former with the carbon selected from aromatic hydrocarbon ring group and at least one aromatic ring of aromatic heterocyclic radical Subnumber be 4~30 alkenyl, with the carbon number selected from aromatic hydrocarbon ring group and at least one aromatic ring of aromatic heterocyclic radical be 4~ 30 alkynyl etc..
A described belowxPreferred instantiation.But, in the present invention, AxIt is not limited to group described below. It should be noted that, in following formula, "-" represents that the key stretched out from the optional position of ring is (same as below.).
(1) aromatic hydrocarbon ring group
[changing 6]
[changing 7]
(2) aromatic heterocyclic radical
[changing 8]
[changing 9]
In above-mentioned formula, E represents NR6, oxygen atom or sulphur atom.Herein, R6Represent hydrogen atom, or methyl, ethyl, propyl group Deng the alkyl that carbon number is 1~6.
[changing 10]
In above-mentioned formula, X, Y, Z represent NR independently of one another7, oxygen atom, sulphur atom ,-SO- or-SO2- (still, exclude Oxygen atom, sulphur atom ,-SO- ,-SO2- situation about each adjoining.).R7With above-mentioned R6Equally, represent hydrogen atom or methyl, ethyl, The carbon numbers such as propyl group are 1~6 alkyl.
[changing 11]
(in above-mentioned formula, X represents implication same as described above.)
(3) there is the alkyl of at least one aromatic ring selected from aromatic hydrocarbon ring group and aromatic heterocyclic radical
[changing 12]
(4) there is the alkenyl of at least one aromatic ring selected from aromatic hydrocarbon ring group and aromatic heterocyclic radical
[changing 13]
(5) there is the alkynyl of at least one aromatic ring selected from aromatic hydrocarbon ring group and aromatic heterocyclic radical
[changing 14]
In above-mentioned AxIn, the aromatic heterocycle that the aromatic hydrocarbyl or carbon number that preferably carbon number is 6~30 are 4~30 Base, any group more preferably as follows,
[changing 15]
[changing 16]
Any group being further preferably as follows.
[changing 17]
AxThe ring being had can have substituent.As such substituent, the halogens such as fluorine atom, chlorine atom can be included Atom, cyano group, the carbon number such as methyl, ethyl, propyl group is 1~6 alkyl, and the carbon number such as vinyl, pi-allyl is 2~6 Alkenyl, the carbon number such as trifluoromethyl is 1~6 haloalkyl, the substituted-amino such as dimethylamino, methoxyl group, ethyoxyl, The carbon numbers such as isopropoxy are 1~6 alkoxy, nitro, the aryl ,-C (=O)-R such as phenyl, naphthyl8,-C (=O)-OR8,- SO2R6Deng.R herein8Represent the virtue that the carbon numbers such as the alkyl that the carbon numbers such as methyl, ethyl are 1~6, or phenyl are 6~14 Base.Wherein, the alkoxy that the alkyl and carbon number that preferably halogen atom, cyano group, carbon number are 1~6 are 1~6.
In addition, AxThe ring being had can have multiple identical or different substituents, and two adjacent substituents also can key It is combined to form ring.The ring of formation can be monocyclic or fused polycycle.
It should be noted that, AxCarbon number for " carbon number " of 2~30 organic group to refer to carbon without substituent former Overall total carbon atom number (the following A of the organic group of sonyIt is same.).
AyRepresent hydrogen atom, can have substituent carbon number for 1~20 alkyl, can have substituent carbon atom Alkenyl that number is 2~20, the carbon number that can have cycloalkyl that the carbon number of substituent be 3~12, can have substituent For 2~20 alkynyl ,-C (=O)-R3、-SO2-R4,-C (=S) NH-R9Or with selected from aromatics hydrocarbon ring and aromatic heterocycle extremely The organic group that the carbon number of a few aromatic ring is 2~30.Herein, R3The carbon number for representing to have substituent is 1~20 Alkyl, can have substituent carbon number be 2~20 alkenyl, can have substituent carbon number be 3~12 ring Alkyl, carbon number are 5~12 aromatic hydrocarbyl, R4Represent that alkyl, carbon number that carbon number is 1~20 are 2~20 Alkenyl, phenyl or 4- aminomethyl phenyls, R9Expression can have the alkyl that the carbon number of substituent is 1~20, can have substituent Carbon number be 2~20 alkenyl, can have substituent carbon number be 3~12 cycloalkyl, can have substituent Carbon number is 5~20 aromatic group.
It is used as AyThe carbon number with substituent be 1~20 alkyl carbon number be 1~20 alkyl, can Include methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, 1- methyl amyls, 1- ethyl pentyl groups, sec-butyl, tertiary fourth Base, n-pentyl, isopentyl, neopentyl, n-hexyl, isohesyl, n-heptyl, n-octyl, n-nonyl, positive decyl, n-undecane base, Dodecyl, n-tridecane base, n-tetradecane base, n-pentadecane base, n-hexadecyl, n-heptadecane base, n-octadecane base, NSC 77136 base, n-eicosane base etc..It is preferably 1 for the carbon number of 1~20 alkyl that can have the carbon number of substituent ~12, more preferably 4~10.
It is used as AyThe carbon number with substituent be 2~20 alkenyl carbon number be 2~20 alkenyl, can Include vinyl, acrylic, isopropenyl, cyclobutenyl, isobutenyl, pentenyl, hexenyl, heptenyl, octenyl, decene Base, hendecene base, laurylene base, tridecylene base, tetradecene base, 15 alkenyls, hexadecylene base, 17 alkenyls, octadecylene base, ten Nine alkenyls, icosa alkene base etc..
It is preferably 2~12 for the carbon number of 2~20 alkenyl that can have the carbon number of substituent.
It is used as AyThe carbon number with substituent be 3~12 cycloalkyl carbon number be 3~12 cycloalkanes Base, can include cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, cyclooctyl etc..
It is used as AyThe carbon number with substituent be 2~20 alkynyl carbon number be 2~20 alkynyl, can Include acetenyl, propinyl, 2-propynyl (propargyl), butynyl, 2- butynyls, 3- butynyls, pentynyl, valerylene Base, hexin base, 5- hexin bases, heptynyl, octynyl, 2- octynyls, n-heptylacetylene base (nonanyl), decynyl (decanyl), 7- Decynyl etc..
It is used as AyThe carbon number with substituent be 1~20 alkyl and can have substituent carbon number be The substituent of 2~20 alkenyl, can include the halogen atoms such as fluorine atom, chlorine atom, and cyano group, dimethylamino etc. replaces ammonia Base, the alkoxy of the carbon number 1~20 such as methoxyl group, ethyoxyl, isopropoxy, butoxy, methoxymethoxy, methoxyl group second The alkoxy that the carbon number for the alkoxy substitution that epoxide etc. is 1~12 with carbon number is 1~12, nitro, phenyl, naphthyl etc. Aryl, the carbon number such as cyclopropyl, cyclopenta, cyclohexyl is 3~8 cycloalkyl, and the carbon such as cyclopentyloxy, cyclohexyl epoxide is former Subnumber is 3~8 cycloalkyl oxy, and the carbon number such as tetrahydrofuran base, THP trtrahydropyranyl, dioxolanyl, alkyl dioxins is 2 ~12 cyclic ether group, the carbon number such as phenoxy group, naphthoxy is 6~14 aryloxy group, trifluoromethyl, pentafluoroethyl group ,- CH2CF3The fluoroalkyl that the carbon number replaced etc. at least one fluorine atom is 1~12, benzofuranyl, chromene Base, benzodioxole base (benzodioxolyl), benzodioxan base ,-C (=O)-R7,-C (=O)-OR7,- SO2R8,-SR10, with-SR10Substituted carbon number is 1~12 alkoxy, hydroxyl etc..Herein, R7And R10Table independently of one another Show cycloalkyl or carbon atom that alkenyl, carbon number that alkyl, carbon number that carbon number is 1~20 are 2~20 are 3~12 Number is 6~12 aromatic hydrocarbyl, R8With above-mentioned R4Represent that alkyl, carbon number that carbon number is 1~20 are 2~20 in the same manner Alkenyl, phenyl or 4- aminomethyl phenyls.
It is used as AyThe carbon number with substituent for 3~12 cycloalkyl substituent, can include fluorine atom, The halogen atoms such as chlorine atom, cyano group, the substituted-amino such as dimethylamino, the alkane that the carbon number such as methyl, ethyl, propyl group is 1~6 Base, the carbon number such as methoxyl group, ethyoxyl, isopropoxy is 1~6 alkoxy, nitro, the aryl, ring third such as phenyl, naphthyl The carbon numbers such as base, cyclopenta, cyclohexyl are 3~8 cycloalkyl ,-C (=O)-R7,-C (=O)-OR7,-SO2R8, hydroxyl etc.. R herein7、R8Represent implication same as described above.
It is used as AyThe carbon number with substituent for 2~20 alkynyl substituent, can include with that can have Alkyl and the substituent phase for the alkenyl that can be 2~20 with the carbon number of substituent that the carbon number of substituent is 1~20 Same substituent.
In AyWith-C (=O)-R3In the group of expression, R3Represent there can be the alkane that the carbon number of substituent is 1~20 Base, can have substituent carbon number be 2~20 alkenyl, can have substituent carbon number be 3~12 cycloalkyl, Carbon number is 5~12 aromatic hydrocarbyl.Their instantiation can be included as above-mentioned AyThe carbon with substituent Alkyl that atomicity is 1~20, the carbon atom that can have alkenyl that the carbon number of substituent be 2~20, can have substituent Number is the group identical group cited by the example of 3~12 cycloalkyl.
In AyWith-SO2-R4In the group of expression, R4Represent alkyl, carbon number that carbon number is 1~20 be 2~ 20 alkenyl, phenyl or 4- aminomethyl phenyls.
R4Carbon number be 1~20 alkyl and carbon number be 2~20 alkenyl instantiation can include with It is used as above-mentioned AyCarbon number be 1~20 alkyl, carbon number be 2~20 alkenyl example cited by group it is identical Group.
It is used as AyThere is the carbon number of at least one aromatic ring selected from aromatics hydrocarbon ring and aromatic heterocycle to have for 2~30 Machine base, can be included and in above-mentioned AxThe group identical group of middle example.
Wherein, as Ay, preferably using hydrogen atom, can have the carbon number of substituent for 1~20 alkyl, can be with taking Alkenyl that Dai Ji carbon number is 2~20, there can be cycloalkyl that the carbon number of substituent be 3~12, there can be substitution Alkynyl ,-C (=the O)-R of the carbon number of base for 2~203、-SO2-R4Or with selected from aromatics hydrocarbon ring and aromatic heterocycle at least The carbon number of one aromatic ring is the group of 2~30 organic basis representation；Further preferably with hydrogen atom, there can be substituent Alkyl that carbon number is 1~20, there can be alkenyl that the carbon number of substituent be 2~20, there can be the carbon of substituent former Cycloalkyl that subnumber is 3~12, the carbon atom that can have alkynyl that the carbon number of substituent be 2~20, can have substituent Aromatic hydrocarbyl that number is 6~12, can have aromatic heterocyclic radical ,-C (=O)-R that the carbon number of substituent be 3~93、-SO2- R4The group of expression.Herein, R3、R4Represent implication same as described above.
It is used as AyThe carbon number with substituent be 1~20 alkyl, can have substituent carbon number be 2 ~20 alkenyl, the substituent can with the alkynyl that the carbon number of substituent is 2~20, preferably halogen atom, cyano group, carbon are former Alkoxy that alkoxy that subnumber is 1~20, the carbon number of the alkoxy for being 1~12 with carbon number substitution are 1~12, benzene Aryloxy group that cyclic ether group that base, cyclohexyl, carbon number are 2~12, carbon number are 6~14, hydroxyl, benzodioxan Base, phenyl sulfonyl, 4- methylphenylsulfonyls, benzoyl ,-SR10.Herein, R10Represent implication same as described above.
It is used as AyThe carbon number with substituent for 3~12 cycloalkyl, can have substituent carbon number For 6~12 aromatic hydrocarbyl, the substituent for the aromatic heterocyclic radical that can be 3~9 with the carbon number of substituent, preferably fluorine original Son, carbon number be 1~6 alkyl, carbon number be 1~6 alkoxy, cyano group.
In addition, AxWith AyIt may then bond together to form ring.As such ring, can include can have the carbon of substituent former The unsaturated carbocyclic that unsaturated heterocycle that subnumber is 4~30, carbon number are 6~30.
The unsaturated carbocyclic that the unsaturated heterocycle for being 4~30 as above-mentioned carbon number, carbon number are 6~30, no spy Different limitation, can be with or without armaticity.For example, ring as shown below can be included.It should be noted that, ring as shown below Display is as in formula (I)
[changing 18]
And the part represented.
[changing 19]
[changing 20]
[changing 21]
(in formula, X, Y, Z represent implication same as described above.)
In addition, these rings can have substituent.As such substituent, it can include and as AxThe aromatic ring being had Substituent and the group identical group of example.
From the viewpoint of the effect desired by the present invention is showed better, AxAnd AyContained pi-electron it is total excellent Elect as more than 4 and less than 24, more preferably more than 6 and less than 20, more preferably more than 6 and 18 with Under.
It is used as AxWith AyPreferred combination, following combination can be included：
(α)AxThe aromatic hydrocarbyl or aromatic heterocyclic radical for being 4~30 for carbon number, AyIt is 3~8 for hydrogen atom, carbon number Cycloalkyl, can have (alkoxy or carbon that alkyl that halogen atom, cyano group, carbon number are 1~6, carbon number are 1~6 Atomicity is 3~8 cycloalkyl) aromatic hydrocarbyl that is 6~12 as the carbon number of substituent, can have (halogen atom, carbon Alkoxy that alkyl that atomicity is 1~6, carbon number are 1~6, cyano group) be 3~9 as the carbon number of substituent virtue Race's heterocyclic radical, can have substituent carbon number be 1~20 alkyl, can have substituent carbon number be 1~20 Alkenyl, there can be an alkynyl that the carbon number of substituent is 2~20, the substituent is that halogen atom, cyano group, carbon number are 1~20 alkoxy, the alkoxy for being 1~12 with carbon number substitution carbon number be 1~12 alkoxy, phenyl, ring Aryloxy group that cyclic ether group that hexyl, carbon number are 2~12, carbon number are 6~14, hydroxyl, benzodioxan base, benzene sulphur Acyl group, benzoyl ,-SR10It is any；With
(β)AxWith AyIt is combined together to form unsaturated heterocycle or unsaturated carbocyclic.Herein, R10Represent same as described above Implication.
It is used as AxWith AyPreferred combination, be following combination：
(γ)AxFor any, A of the group with having structureyThe cycloalkyl for being 3~8 for hydrogen atom, carbon number, Can have that (alkoxy or carbon number that alkyl that halogen atom, cyano group, carbon number are 1~6, carbon number are 1~6 are 3 ~8 cycloalkyl) be 6~12 as the carbon number of substituent aromatic hydrocarbyl, can have (halogen atom, carbon number are 1 ~6 alkyl, the alkoxy that carbon number is 1~6, cyano group) be 3~9 as the carbon number of substituent aromatic heterocyclic radical, Can have substituent carbon number be 1~20 alkyl, can have substituent carbon number be 1~20 alkenyl, can have The carbon number of substituted base is 2~20 alkynyl, and the substituent is the alkane that halogen atom, cyano group, carbon number are 1~20 Alkoxy that epoxide, the carbon number of the alkoxy for being 1~12 with carbon number substitution are 1~12, phenyl, cyclohexyl, carbon are former Aryloxy group that cyclic ether group that subnumber is 2~12, carbon number are 6~14, hydroxyl, benzodioxan base, benzenesulfonyl, benzene first Acyl group ,-SR10It is any.Herein, R10Represent implication same as described above.
[changing 22]
[changing 23]
(in formula, X, Y represent implication same as described above.)
It is used as AxWith AyParticularly preferred combination, be following combination：
(δ)AxFor any, A of the group with having structureyThe cycloalkyl for being 3~8 for hydrogen atom, carbon number, can With (alkoxy or carbon number that alkyl that halogen atom, cyano group, carbon number are 1~6, carbon number are 1~6 be 3~ 8 cycloalkyl) be 6~12 as the carbon number of substituent aromatic hydrocarbyl, can have (halogen atom, carbon number be 1~ 6 alkyl, the alkoxy that carbon number is 1~6, cyano group) be 3~9 as the carbon number of substituent aromatic heterocyclic radical, can Alkyl that carbon number with substituent is 1~20, there can be alkenyl that the carbon number of substituent be 1~20, can have The carbon number of substituent is 2~20 alkynyl, and the substituent is the alcoxyl that halogen atom, cyano group, carbon number are 1~20 Base, the alkoxy for being 1~12 with carbon number substitution carbon number be 1~12 alkoxy, phenyl, cyclohexyl, carbon atom Aryloxy group that cyclic ether group that number is 2~12, carbon number are 6~14, hydroxyl, benzodioxan base, benzenesulfonyl, benzoyl Base ,-SR10It is any.In following formula, X represents implication same as described above.Herein, R10Represent implication same as described above.
[changing 24]
A1Represent there can be the trivalent aromatic group of substituent.As trivalent aromatic group, can for trivalent carbon-ring type aromatic group or Trivalent hetero ring type aromatic group.From the viewpoint of the effect desired by the present invention is showed better, preferably trivalent carbon-ring type is fragrant Race's base, more preferably trivalent phenyl ring base or trivalent naphthalene nucleus base, trivalent phenyl ring base or trivalent naphthalene nucleus base shown in further preferred following formula.
It should be noted that, in following formula, in order that bond styles are clearer and more definite, substituent Y is recorded for convenient1、Y2(Y1、 Y2Represent implication same as described above.It is same as below.).
[changing 25]
Wherein, as A1, the group more preferably represented with following shown formula (A11)~(A25), further preferably with formula (A11), the group that (A13), (A15), (A19), (A23) are represented, the group particularly preferably represented with formula (A11), (A23).
[changing 26]
It is used as A1The substituent that can have of trivalent aromatic group, can include with as above-mentioned AXAromatic group substituent And the group identical group of example.It is used as A1, the preferred group without substituent.
A2、A3Represent there can be the divalence alicyclic type hydrocarbon that the carbon number of substituent is 3~30 independently of one another.
As the divalence alicyclic type hydrocarbon that carbon number is 3~30, the cycloalkanes two that carbon number is 3~30 can be included Base, carbon number are 10~30 divalence ester ring type condensed ring radical etc..
As the cycloalkanes diyl that carbon number is 3~30, cyclopropane diyl, cyclobutane -1,2- diyl, ring fourth can be included The cyclobutane diyl such as alkane -1,3- diyl, the pentamethylene diyl such as pentamethylene -1,2- diyl, pentamethylene -1,3- diyl, hexamethylene -1, The hexamethylene diyls such as 2- diyls, hexamethylene -1,3- diyl, hexamethylene-Isosorbide-5-Nitrae-diyl, cycloheptane -1,2- diyl, cycloheptane -1, The cycloheptane diyls such as 3- diyls, cycloheptane-Isosorbide-5-Nitrae-diyl, cyclooctane -1,2- diyl, cyclooctane -1,3- diyl, cyclooctane -1, The cyclooctane diyls such as 4- diyls, cyclooctane -1,5- diyl, cyclodecane -1,2- diyl, cyclodecane -1,3- diyl, cyclodecane -1, The cyclodecane diyls such as 4- diyls, cyclodecane -1,5- diyl, cyclododecane -1,2- diyl, cyclododecane -1,3- diyl, ring 12 The cyclododecane diyls such as alkane-Isosorbide-5-Nitrae-diyl, cyclododecane -1,5- diyl, ring tetradecane -1,2- diyl, ring tetradecane -1,3- bis- The ring tetradecane diyls, ring 20 such as base, the ring tetradecane-Isosorbide-5-Nitrae-diyl, ring tetradecane -1,5- diyl, ring tetradecane -1,7- diyl Ring eicosane diyls such as alkane -1,2- diyls, ring eicosane -1,10- diyls etc..
As the divalence ester ring type condensed ring radical that carbon number is 10~30, naphthalane -2,5- diyl, naphthalane -2 can be included, The naphthalane diyl such as 7- diyls, the adamantane diyl such as adamantane -1,2- diyl, adamantane -1,3- diyl, bicyclic [2.2.1] heptane - Bicyclic [2.2.1] heptane two such as 2,3- diyls, bicyclic [2.2.1] heptane -2,5- diyls, bicyclic [2.2.1] heptane -2,6- diyls Base etc..
These divalence alicyclic type hydrocarbons can have substituent at an arbitrary position.As substituent, can include with as upper State AXAromatic group substituent and the group identical group of example.
Wherein, as A2、A3, preferably carbon number be 3~12 divalence alicyclic type hydrocarbon, more preferably carbon number be 3~ 12 cycloalkanes diyl, further preferably with following formula (A31)~(A34)
[changing 27]
The group of expression, the group particularly preferably represented with above-mentioned formula (A32).
Above-mentioned carbon number be 3~30 divalence alicyclic type hydrocarbon, according to Y1、Y3(or Y2、Y4) bonding carbon atom The difference of steric configuration, may be present cis type, the stereoisomer of trans type.For example, in the situation of hexamethylene-Isosorbide-5-Nitrae-diyl Under, it is as follows, the isomers (A32a) of cis type and the isomers (A32b) of trans type may be present.
[changing 28]
In the present invention, it can be cis type or trans type, or can be the isomer mixture of cis type and trans type；But It is advantageous to more preferably trans type because orientation is good for trans type or cis type.
A4、A5Represent there can be the divalent aromatic radical that the carbon number of substituent is 6~30 independently of one another.
A4、A5Aromatic group can be monocyclic aromatic group or polycyclic aromatic group.
It is used as A4、A5Preferred instantiation, following groups can be included.
[changing 29]
Above-mentioned A4、A5Divalent aromatic radical can have substituent at an arbitrary position.As the substituent, halogen can be included Alkoxy that alkyl that plain atom, cyano group, hydroxyl, carbon number are 1~6, carbon number are 1~6, nitro ,-C (=O)-OR8 Base etc..R herein8The alkyl for being 1~6 for carbon number.Wherein, preferably halogen atom, carbon number are 1~6 alkyl, alcoxyl Base.In addition, being used as halogen atom more preferably fluorine atom；It is used as the alkyl that carbon number is 1~6, more preferably methyl, ethyl, third Base；It is used as alkoxy, more preferably methoxyl group, ethyoxyl.
Wherein, from the viewpoint of the effect desired by the present invention is showed better, A4、A5Independently of one another more preferably For that can have the group that is represented with following formula (A41), (A42) and (A43) of substituent, particularly preferably can with substituent with The group that formula (A41) is represented.
[changing 30]
Q1Represent hydrogen atom, there can be the alkyl that the carbon number of substituent is 1~6.
The alkyl for being 1~6 as the carbon number can with substituent, can be included and in above-mentioned AXThe group of middle example Identical group.
Wherein, Q1It is preferred that hydrogen atom or the alkyl that carbon number is 1~6, more preferably hydrogen atom and methyl.
The polymerizable compound of the present invention can for example be prepared by reaction as shown below.
[changing 31]
(in formula, Y1~Y8、G1、G2、Z1、Z2、Ax、Ay、A1~A5、Q1Represent implication same as described above.)
That is, the hydrazine compound (hydrazine compound (3)) represented with formula (3) and the carbonyls (carbonyl represented with formula (4) are made Compound (4)) with [hydrazine compound (3):Carbonyls (4)] molar ratio computing 1:2~2:1st, preferably 1:1.5~1.5:1 Ratio under react, thus high selectivity and the polymerization of the invention represented with formula (I) as target can be prepared in high yield Property compound.
In this case, the organic acids such as (±) -10- camphorsulfonic acids, p-methyl benzenesulfonic acid can be added, hydrochloric acid, sulfuric acid etc. are inorganic The acid catalysts such as acid and reacted.It is possible to shorten the reaction time by adding acid catalyst, improves yield.Rubbed relative to 1 Your carbonyls (4), the addition of acid catalyst is usually 0.001~1 mole.In addition, acid catalyst can be added directly Or added as solution obtained by being dissolved in appropriate solvent.
As solvent used in the reaction, if being then not particularly limited to reacting inactive solvent.For example, can enumerate Go out the alcohols solvents such as methanol, ethanol, normal propyl alcohol, isopropanol, n-butanol, isobutanol, sec-butyl alcohol, the tert-butyl alcohol, ether, tetrahydrochysene furan Mutter, the ether solvent, ethyl acetate, propyl acetate, propionic acid such as 1,2- dimethoxy-ethanes, the dioxane of Isosorbide-5-Nitrae-, cyclopentyl-methyl ether The esters solvents such as methyl esters, the aromatic hydrocarbons solvent such as benzene,toluene,xylene, the aliphatic hydrocarbon such as pentane, n-hexane, normal heptane is molten Agent, the amide solvent, dimethyl sulfoxide (DMSO), ring such as DMF, 1-METHYLPYRROLIDONE, HPT The sulfur-bearing class solvent such as fourth sulfone, and the mixed solvent being made up of they two or more etc..
Wherein, the preferred mixed solvent of alcohols solvent, ether solvent and alcohols solvent and ether solvent.
The usage amount of solvent is not particularly limited, it is contemplated that species, reaction scale of used compound etc. and it is suitable really It is fixed, but the hydrazine compound (3) relative to 1g, usually 1~100g.
React and successfully carried out within the temperature range of -10 DEG C of boiling points to used solvent.Although that respectively reacts is anti- Also depend on reaction scale between seasonable, but usually several minutes to a few hours.
Hydrazine compound (3) can be prepared as follows.
[changing 32]
(in formula, Ax、AyRepresent implication same as described above.X represents halogen atom, mesyloxy, tolysulfonyl The leaving groups such as epoxide.)
That is, in appropriate solvent, make the compound represented with formula (2a) with hydrazine (1) with (compound (2a):Hydrazine (1)) Molar ratio computing is 1:1~1:20th, preferably 1:2~1:10 times reactions, can obtain corresponding hydrazine compound (3a), and then make hydrazine chemical combination Thing (3a) reacts with the compound represented with formula (2b), so as to can obtain hydrazine compound (3).
As hydrazine (1), usually using monohydrate.Commercially available product can be used directly in hydrazine (1).
As solvent used in the reaction, if being then not particularly limited to reacting inactive solvent.For example, can enumerate Go out the alcohols solvents such as methanol, ethanol, normal propyl alcohol, isopropanol, n-butanol, isobutanol, sec-butyl alcohol, the tert-butyl alcohol, ether, tetrahydrochysene furan Mutter, the ether solvent such as 1,2- dimethoxy-ethanes, the dioxane of Isosorbide-5-Nitrae-, cyclopentyl-methyl ether, the aromatic hydrocarbon such as benzene,toluene,xylene Class solvent, the aliphatic hydrocarbon solvents, DMF, 1-METHYLPYRROLIDONE, six such as pentane, n-hexane, normal heptane The amide solvents such as methyl acid phosphate triamide, the sulfur-bearing class solvent such as dimethyl sulfoxide (DMSO), sulfolane, and by their two or more structure Into mixed solvent etc..
Wherein, the preferred mixed solvent of alcohols solvent, ether solvent and alcohols solvent and ether solvent.
The usage amount of solvent is not particularly limited, it is contemplated that species, reaction scale of used compound etc. and it is suitable really It is fixed, but the hydrazine relative to 1g, usually 1~100g.
React and successfully carried out within the temperature range of -10 DEG C of boiling points to used solvent.Although that respectively reacts is anti- Also depend on reaction scale between seasonable, but usually several minutes to a few hours.
In addition, hydrazine compound (3) can also use currently known method as follows, made by reducing diazol (5) It is standby.
[changing 33]
In formula (5), Ax、AyRepresent implication same as described above.X-Be denoted as diazonium ion balance it is cloudy from Son.It is used as X-, such as can include hexafluorophosphate ion, fluoboric acid ion, chloride ion, sulfate ion it is inorganic it is cloudy from Son, polyfluoroalkanoic acids ion, Polyfluoroalkyl azochlorosulfonate acid ion, tetraphenylboronic acid ion, aromatic carboxylic acid's ion, aromatic sulfonic acid ion Deng organic anion etc..
As reducing agent used in above-mentioned reaction, metal salt back agent can be included.
Metal salt back agent is usually the compound containing low valence metal or is made up of metal ion and hydride source Compound (with reference to " Yuki Gosei Jikkenhou Handbook (organic synthetic experiment method handbook) " nineteen ninety corporations' method Bian Wanshan Co., Ltd. of people's Synthetic Organic Chemistry association issues page 810).
As metal salt back agent, NaAlH can be included4、NaAlHp(Or)q(p, q represent independently of one another 1~3 it is whole Number, p+q=4.R represents the alkyl that carbon number is 1~6.)、LiAlH4、iBu2AlH、LiBH4、NaBH4、SnCl2、CrCl2、 TiCl3Deng.
Can be using known reaction condition in reduction reaction.For example can be in Japanese Unexamined Patent Publication 2005-336103 publications, new The Nian Wanshan Co., Ltd. of experimental chemistry lecture 1978 issues volume 14, the Nian Wanshan Co., Ltd. of experimental chemistry lecture 1992 distribution the Reacted under conditions of the documents such as volume 20 are described.
In addition, diazol (5) can be prepared by compounds such as aniline by conventional method.
Carbonyls (4) can typically by any combination ehter bond (- O-), ester bond (- C (=O)-O- ,-O-C (= O) -), the formation reaction of carbonic acid ester bond (- O-C (=O)-O-) and amido link (- C (=O)-NH- ,-NH-C (=O) -), will have A variety of known compounds of desired structure are suitably bonded modification to prepare.
The formation of ehter bond can be carried out as follows.
(i) will be with formula：(hal represents halogen atom to D1-hal.It is same as below.) represent compound with formula：D2-OMet (Met represents alkali metal (predominantly sodium).It is same as below.) represent compound mix and be condensed (Williamson conjunction Into).It should be noted that, in formula, D1 and D2 represent that arbitrary organic group is (same as below.)
(ii) will be with formula：Compound that D1-hal is represented with formula：The compound that D2-OH is represented is in sodium hydroxide, hydrogen-oxygen Mix and be condensed in the presence of the alkali such as change potassium.
(iii) will be with formula：(J represents epoxy radicals to D1-J.) represent compound with formula：The compound that D2-OH is represented exists Mix and be condensed in the presence of the alkali such as sodium hydroxide, potassium hydroxide.
(iv) will be with formula：(OFN represents the group with unsaturated bond to D1-OFN.) represent compound with formula：D2- The compound that OMet is represented mixes in the presence of the alkali such as sodium hydroxide, potassium hydroxide and carries out addition reaction.
(v) will be with formula：Compound that D1-hal is represented with formula：The compound that D2-OMet is represented is in copper or stannous chloride In the presence of mix and be condensed (Ullmann condensations).
The formation of ester bond and amido link can be carried out as follows.
(vi) make with formula：Compound that D1-COOH is represented with formula：D2-OH or D2-NH2The compound of expression is in dehydration Dehydrating condensation in the presence of condensing agent (N, N- dicyclohexyl carbodiimide etc.).
(vii) by making halogenating agent and with formula：The compound that D1-COOH is represented is had an effect, and is obtained with formula：D1-CO- The compound that hal is represented, makes the compound and with formula：D2-OH or D2-NH2The compound of expression is reacted in the presence of a base.
(viii) by making acid anhydrides and with formula：The compound that D1-COOH is represented is had an effect, and is obtained after mixed acid anhydride, Make with formula：D2-OH or D2-NH2The compound of expression and the mixed anhydride reaction.
(ix) make with formula：Compound that D1-COOH is represented with formula：D2-OH or D2-NH2The compound of expression is urged in acid Dehydrating condensation in the presence of agent or base catalyst.
The carbonyls (4) of the present invention can specifically be prepared by the method shown in following reaction equation.
[changing 34]
(in formula, Y1~Y8、G1、G2、Z1、Z2、A1~A5And Q1Represent implication same as described above.L1、L2Expression hydroxyl, The leaving groups such as halogen atom, mesyloxy, tolysulfonyl epoxide.-Y1aRepresent and-L1Reaction is so as to form-Y1- base Group ,-Y2aRepresent to react with-L2 to form-Y2- group.)
That is, by using currently known ehter bond (- O-), ester bond (- C (=O)-O- ,-O-C (=O) -) or carbonic acid ester bond The formation reaction of (- O-C (=O)-O-), make the compound represented with formula (6d) successively with the compound that is represented with formula (7a) and with The compound reaction that formula (7b) is represented, can prepare the carbonyls (4) of the present invention.
More specifically, wherein Y described below1For with Y11Group that-C (=O)-O- is represented and with formula：Z2-Y8-G2- Y6-A5-Y4-A3-Y2- represent group with formula：Z1-Y7-G1-Y5-A4-Y3-A2-Y1- group identical the compound represented The preparation method of (4 ').
[changing 35]
(in formula, Y3、Y5、Y7、G1、Z1、A1、A2、A4、Q1And L1Represent implication same as described above.Y11Represent Y11- C (= O)-O- formation Y1Group.Y1Represent implication same as described above.)
In above-mentioned reaction, make the dihydroxy compounds (compound (6)) represented with formula (6) and the change represented with formula (7) Compound (compound (7)) is with (compound (6):Compound (7)) molar ratio computing 1:2~1:4th, preferably 1:2~1:3 ratio Lower reaction, thus high selectivity and can obtain compound (4 ') as target in high yield.
The L in compound (7) is formula (7)1In the case of compound (carboxylic acid) for hydroxyl, by 1- ethyl -3- (3- Dimethylamino-propyl) reacted in the presence of the dehydrating condensation agent such as carbodiimide hydrochloride, dicyclohexyl carbodiimide, can Obtain object.
Compound (7) relative to 1 mole, the usage amount of dehydrating condensation agent is usually 1~3 mole.
In addition, being L in formula (7) in compound (7)1In the case of compound (carboxylic acid) for hydroxyl, by methylsulfonyl The alkali such as the sulfonic acid halides such as chlorine, paratoluensulfonyl chloride and triethylamine, diisopropyl ethyl amine, pyridine, 4- (dimethylamino) pyridine is present It is lower to be reacted, it also can obtain object.
Compound (7) relative to 1 mole, the usage amount of sulfonic acid halide is usually 1~3 mole.
Compound (7) relative to 1 mole, the usage amount of alkali is usually 1~3 mole.
In this case, the L in above-mentioned formula (7) is separated1It is next for compound (mixed acid anhydride) progress of sulfonyloxy Reaction.
In addition, being L in formula (7) in compound (7)1In the case of compound (carboxylic acid halides) for halogen atom, by alkali In the presence of reacted, can obtain object.
As used alkali, the organic bases such as triethylamine, pyridine, sodium hydroxide, sodium carbonate, sodium acid carbonate etc. can be included Inorganic base.
Compound (7) relative to 1 mole, the usage amount of alkali is usually 1~3 mole.
As solvent used in above-mentioned reaction, the chlorine class solvent such as can include chloroform, dichloromethane, N- methyl pyrroles The amide solvents such as pyrrolidone, DMF, DMA, HPT, Isosorbide-5-Nitrae-two The ethers such as oxane, cyclopentyl-methyl ether, tetrahydrofuran, oxinane, DOX, dimethyl sulfoxide (DMSO), sulfolane etc. contain Sulphur class solvent, the aromatic hydrocarbons solvent such as benzene,toluene,xylene, the aliphatic hydrocarbon solvents, ring penta such as pentane, n-hexane, normal octane The ester ring type varsol such as alkane, hexamethylene, and two or more mixed solvent constituted by these solvents etc..
The usage amount of solvent is not particularly limited, it is contemplated that the suitably determination such as species, reaction scale of used compound, But the hydroxy compounds (6) relative to 1g, usually 1~50g.
Compound (6) is generally known material, can be prepared by known method.
For example, can be prepared by the method shown in following reaction equation (with reference to No. WO2009/042544 and The Journal of Organic Chemistry, 2011,76,8082-8087 etc..).Also can will be commercially available as compound (6) Product is purified and used as needed.
[changing 36]
(in formula, A1、Q1Represent implication same as described above, A1aExpression forms A by formylated or acylation1Divalent Aromatic group, R ' represents the alcoxyl that the carbon numbers such as alkyl, the methoxy that the carbon numbers such as methyl, ethyl are 1~6 are 2~6 The protection group of the hydroxyls such as base alkyl.)
That is, the hydroxyl alkane for the dihydroxy compounds (Isosorbide-5-Nitrae-dihydroxy benzenes, Isosorbide-5-Nitrae-dihydroxy naphthlene etc.) that will be represented with formula (6a) Base, is obtained after the compound that is represented with formula (6b), by the ortho position of OR ' bases by known method formylated or acylation, thus The compound represented with formula (6c) is obtained, by the way that the compound is deprotected into (dealkylation), the chemical combination as target can be obtained Thing (6).
In addition, as compound (6), directly can use by commercially available product or purify and use as needed.
Compound (7) is generally known compound, can be by arbitrarily combining ehter bond (- O-), ester bond (- C (=O)-O- ,-O- C (=O) -), the formation reaction of carbonic acid ester bond (- O-C (=O)-O-) and amido link (- C (=O)-NH- ,-NH-C (=O) -), will A variety of known compounds with desired structure are suitably bonded modification to prepare.
For example, in the case where compound (7) is the compound (compound (7 ')) represented with following formula (7 '), can be used The dicarboxylic acids (compound (9 ')) represented with formula (9 '), is prepared as follows.
[changing 37]
(in formula, Y5、Y7、G1、Z1、A2、A4、Y11Represent implication same as described above.Y12Expression-O-C (=O)-Y12Shape Into Y3Group.R represents the alkyl such as methyl, ethyl, and phenyl, p-methylphenyl etc. can have the aryl of substituent.)
First, compound (9 ') and the sulfonic acid chloride that is represented with formula (10) are made in alkali such as triethylamine, 4- (dimethylamino) pyridines In the presence of react.
Then, the alkali such as compound (8) and triethylamine, 4- (dimethylamino) pyridine are added into reactant mixture to carry out instead Should.
Relative to the compound (9 ') of 1 equivalent, the usage amount of sulfonic acid chloride is usually 0.5~0.7 equivalent.
Relative to the compound (9 ') of 1 equivalent, the usage amount of compound (8) is usually 0.5~0.6 equivalent.
Relative to the compound (3) of 1 equivalent, the usage amount of alkali is usually 0.5~0.7 equivalent.
Reaction temperature is 20~30 DEG C, although the reaction time depends on reaction scale etc., is several minutes~a few hours.
As solvent used in above-mentioned reaction, it can include as workable molten when preparing above-claimed cpd (4 ') Agent and the solvent of example.Wherein, preferred ethers.
The usage amount of solvent is not particularly limited, it is contemplated that species, reaction scale of used compound etc. and it is suitable really It is fixed, but the compound (9 ') relative to 1g, usually 1~50g.
In all reactions, the common post-processing operation in Synthetic Organic Chemistry is carried out after the completion of reaction, according to Need, it is possible to implement isolation and purification method known to column chromatography, recrystallization method, way of distillation etc., thus separate object.
It can be identified as the structure of the compound of target by measure, elementary analysis of H NMR spectroscopy, IR spectrums, mass spectrum etc. etc..
2) polymerizable composition, polymerizable composition
The 2nd embodiment of the present invention is the polymerism combination of the polymerizable compound containing the present invention and polymerization initiator Thing.The blend polymer initiator from the viewpoint of the polymerisation of polymerizable compound for being more effectively carried out the present invention.
As used polymerization initiator, as long as the species choosing for the polymerizable group being had according to polymerizable compound Select and use suitable polymerization initiator.For example, using free radical if polymerizable group is free-radical polymerised group Polymerization initiator, if anionic polymerisation group then uses anionic polymerization initiator, if cationic polymerization Property group then use cationic polymerization initiators.
As radical polymerization initiator, thermal free radical initiator, it is that can trigger polymerism by heating generation The compound of the active species of the polymerization of compound；With optical free radical initiator, it is to pass through luminous ray, ultraviolet (i rays Deng), far ultraviolet, electron ray, X-ray etc. expose the exposure of light to the open air and produce the activity of the polymerization that can trigger polymerizable compound The compound of species；It can be used, but preferably use optical free radical initiator.
As optical free radical initiator, acetophenone compounds, bisglyoxaline class compound, triazines chemical combination can be included Thing, O- acyl groups oxime compound, salt compounds, benzoin class compound, benzophenone compound, α-diones chemical combination Thing, multinuclear quinones, Xanthene ketone compound, weight nitrogen compound, sulfimide (imide sulfonate) class Compound etc..These compounds is produce living radical or active acid or living radical and active acid by exposure Both compositions.Optical free radical initiator can be used alone a kind of or be used two or more combination.
As the instantiation of acetophenone compounds, 2- hydroxy-2-methyl -1- phenyl-propane -1- ketone, 2- can be included Methyl isophthalic acid-[4- (methyl mercapto) phenyl] -2- morpholino propane -1- ketone, 2- benzyl -2- dimethylaminos -1- (4- morpholino benzene Base) butane -1- ketone, 1- hydroxycyclohexylphenylketones, 2,2- dimethoxy -1,2- diphenylethane -1- ketone, 1,2- pungent two Ketone, 2- benzyl -2- dimethylamino -4 '-morpholino butyrophenones etc..
As the instantiation of bisglyoxaline class compound, 2,2 '-bis- (2- chlorphenyls) -4,4 ', 5,5 '-four can be included (4- carboethoxyphenyls) -1,2 '-bisglyoxaline, 2,2 '-bis- (2- bromophenyls) -4,4 ', 5,5 '-four (4- ethoxy carbonyl benzene Base) -1,2 '-bisglyoxaline, 2,2 '-bis- (2- chlorphenyls) -4,4 ', 5,5 '-tetraphenyl -1,2 '-bisglyoxaline, 2,2 '-bis- (2,4- bis- Chlorphenyl) -4,4 ', 5,5 '-tetraphenyl -1,2 '-bisglyoxaline, 2,2 '-bis- (2,4,6- trichlorophenyls) -4,4 ', 5,5 '-four benzene Base -1,2 '-bisglyoxaline, 2,2 '-bis- (2- bromophenyls) -4,4 ', 5,5 '-tetraphenyl -1,2 '-bisglyoxaline, 2,2 '-bis- (2,4- bis- Bromophenyl) -4,4 ', 5,5 '-tetraphenyl -1,2 '-bisglyoxaline, 2,2 '-bis- (2,4,6- tribromos phenyl) -4,4 ', 5,5 '-four benzene Base -1,2 '-bisglyoxaline etc..
In the present invention, in the case where using bisglyoxaline class compound as Photoepolymerizationinitiater initiater, and with hydrogen donor by In can further improve sensitivity and it is preferred that.
" hydrogen donor " refers to can supply the chemical combination of hydrogen atom to the free radical produced by exposure by bisglyoxaline class compound Thing.It is used as hydrogen donor, sulfur alcohol compound, aminated compounds preferably defined below etc..
As sulfur alcohol compound, 2-mercaptobenzothiazole, 2- mercaptobenzoxazoles, 2- sulfydryl benzo miaows can be included Azoles, 2,5- dimercapto -1,3,4- thiadiazoles, 2- sulfydryl -2,5- dimethyl aminopyridines etc..As aminated compounds, it can enumerate Bis- (diethylamino) benzophenone of-bis- (dimethylamino) benzophenone, 4,4 '-that go out 4,4 ', 4- diethyl aminos benzoylformaldoxime, 4- dimethylaminos propiophenone, EDMAB, 4- dimethylaminobenzoic acids, 4- dimethylaminobenzonitriles Deng.
As compound in triazine class, the double (trichlorines of 2,4,6- tri- (trichloromethyl)-s-triazine, 2- methyl -4,6- can be included Methyl)-s-triazine, 2- [2- (5- methylfuran -2- bases) vinyl] -4,6- double (trichloromethyl)-s-triazine, 2- [2- (furans Mutter -2- bases) vinyl] -4,6- double (trichloromethyl)-s-triazine, 2- [2- (4- diethylamino -2- aminomethyl phenyls) ethene Base] double (the trichloromethyl)-s-triazine of -4,6-, 2- [2- (3,4- Dimethoxyphenyls) vinyl] -4,6- double (trichlorophenyls) - Double (the trichloromethyl)-s-triazine of s-triazine, 2- (4- methoxyphenyls) -4,6-, 2- (4- ethoxystyrenes base) -4,6- are double Double (trichloromethyl)-s-triazine of (trichloromethyl)-s-triazine, 2- (4- n-butoxyphenyls) -4,6- etc. have halogenated methyl Compound in triazine class.
As the instantiation of O- acyl group oxime compounds, 1- [4- (thiophenyl) phenyl]-heptane -1,2- bis- can be included Ketone 2- (O- benzoyl oximes), 1- [4- (thiophenyl) phenyl]-octane -1,2- diketone 2- (O- benzoyl oximes), 1- [4- (benzene Formoxyl) phenyl]-octane -1,2- diketone 2- (O- benzoyl oximes), 1- [9- ethyls -6- (2- methyl benzoyls) -9H- clicks Azoles -3- bases]-ethyl ketone 1- (O- acetyl group oxime), 1- [9- ethyls -6- (3- methyl benzoyls) -9H- carbazole -3- bases]-ethyl ketone 1- (O- acetyl group oxime), 1- (9- ethyl -6- benzoyl -9H- carbazole -3- bases)-ethyl ketone 1- (O- acetyl group oxime), ethyl ketone -1- [9- Ethyl -6- (2- methyl -4- tetrahydrofuran bases benzoyl) -9.H.- carbazole -3- bases] -1- (O- acetyl group oxime), ethyl ketone -1- [9- ethyls -6- (2- methyl -4- THP trtrahydropyranyls benzoyl) -9.H.- carbazole -3- bases] -1- (O- acetyl group oxime), ethyl ketone - 1- [9- ethyls -6- (2- methyl -5- tetrahydrofuran bases benzoyl) -9.H.- carbazole -3- bases] -1- (O- acetyl group oxime), second Ketone -1- [9- ethyls -6- (2- methyl -5- THP trtrahydropyranyls benzoyl) -9.H.- carbazole -3- bases] -1- (O- acetyl group oxime), Ethyl ketone -1- [9- ethyls -6- { 2- methyl -4- (2,2- dimethyl -1,3- dioxolanyls) benzoyl } -9.H.- carbazoles -3- Base] -1- (O- acetyl group oxime), ethyl ketone -1- [9- ethyls -6- (2- methyl -4- tetrahydrofuran base methoxybenzoyls base) -9.H.- Carbazole -3- bases] -1- (O- acetyl group oxime), ethyl ketone -1- [9- ethyls -6- (2- methyl -4- THP trtrahydropyranyl methoxybenzoyls Base) -9.H.- carbazole -3- bases] -1- (O- acetyl group oxime), ethyl ketone -1- [9- ethyls -6- (2- methyl -5- tetrahydrofuran base methoxies Base benzoyl) -9.H.- carbazole -3- bases] -1- (O- acetyl group oxime), ethyl ketone -1- [9- ethyls -6- (2- methyl benzoyls) - 9H- carbazole -3- bases] -1- (O- acetyl group oxime), ethyl ketone -1- [9- ethyls -6- (2- methyl -5- THP trtrahydropyranyl methoxybenzene first Acyl group) -9.H.- carbazole -3- bases] -1- (O- acetyl group oxime), ethyl ketone -1- [9- ethyls -6- 2- methyl -4- (2,2- dimethyl - 1,3- dioxolanyls) methoxybenzoyl base } -9.H.- carbazole -3- bases] -1- (O- acetyl group oxime) etc..
Commercially available product also can be used directly in optical free radical initiator.As instantiation, the business of BASF AG can be included The name of an article：Irgacure907, trade name：Irgacure184, trade name：Irgacure369, trade name：Irgacure651, business The name of an article：Irgacure819, trade name：Irgacure907 and trade name：The commodity of Irgacure OXE02, ADEKA company systems Name：Adekaoptomer N1919 etc..
As above-mentioned anionic polymerization initiator, alkyl lithium compounds can be included；Biphenyl, naphthalene, the single lithium salts or list of pyrene Sodium salt；Multifunctional initiators such as dilithium salt, three lithium salts etc..
In addition, as above-mentioned cationic polymerization initiators, the matter such as sulfuric acid, phosphoric acid, perchloric acid, trifluoromethanesulfonic acid can be included It is sub sour, the lewis acid of boron trifluoride, aluminium chloride, titanium tetrachloride, butter of tin etc, aromatics salt or aromatics salt are with reducing The paralled system of agent.
These polymerization initiators can be used alone a kind of or be used two or more combination.
In the polymerizable composition, polymerizable composition of the present invention, relative to the polymerizable compound of 100 parts by weight, polymerization initiator is mixed Mixed ratio is usually 0.1~30 parts by weight, preferably 0.5~10 parts by weight.
In addition, in the polymerizable composition, polymerizable composition of the present invention, in order to adjust surface tension, preferably blending surfactant.Make For the surfactant, it is not particularly limited, but generally preferably nonionic class surfactant.It is used as the nonionic class surface Activating agent, as long as using commercially available product, for example, the nonionic class as molecular weight for the oligomer of thousands of left and right can be included Surfactant (such as AGC Seimi Chemical Co., Ltd. KH-40) etc..In the polymerizable composition, polymerizable composition of the present invention In, relative to the polymerizable compound of 100 parts by weight, the mixing proportion of surfactant is usually 0.01~10 parts by weight, excellent Elect 0.1~2 parts by weight as.
In addition, the present invention polymerizable composition, polymerizable composition in, can also further blend the copolymerizable monomer of others described later, Metal, metal complex, dyestuff, pigment, fluorescent material, phosphor material, levelling agent (leveling agent), thixotropic agent, glue The metal oxidation such as solidifying agent, polysaccharide, ultra-violet absorber, infrared absorbent, antioxidant, ion exchange resin, titanium oxide The others additive such as thing.It is other relative to the polymerizable compound of 100 parts by weight in the polymerizable composition, polymerizable composition of the present invention Additive mixing proportion typically respectively 0.1~20 parts by weight.
The present invention polymerizable composition, polymerizable composition generally can by by the present invention polymerizable compound, polymerization initiator and according to The ormal weight of the other additives needed in appropriate organic solvent mixed dissolution and prepare.
As used organic solvent, the ketones such as cyclopentanone, cyclohexanone, MEK, butyl acetate, acetic acid can be included The acetates such as pentyl ester, the halogenated hydrocarbon, the dioxane of Isosorbide-5-Nitrae-, cyclopentyl-methyl ether, tetrahydrochysene such as chloroform, dichloromethane, dichloroethanes Ethers such as furans, oxinane, 1,3- dioxolanes etc..
As described later, the polymerizable composition, polymerizable composition as above obtained is used as the macromolecule of the present invention or the system of optically anisotropic body Standby raw material is useful.
3) macromolecule
Macromolecule or (2) obtained from the polymerizable compound of the present invention polymerize by the 3rd embodiment of the present invention for (1) By macromolecule obtained from the polymerizable composition, polymerizable composition polymerization of the present invention.
Herein, " polymerization " refers to the chemical reaction of the broad sense comprising cross-linking reaction in addition to common polymerisation, also.
(1) by macromolecule obtained from the polymerizable compound polymerization of the present invention
As macromolecule obtained from the polymerizable compound polymerization by the present invention, the polymerism of the present invention can be included The polymerism chemical combination of the homopolymer of compound, two or more copolymer constituted by polymerizable compound of the invention or the present invention The copolymer of thing and other copolymerizable monomers.
As the copolymerizable monomer of above-mentioned others, it is not particularly limited, for example, 4- (2- methacryloxypropyls can be included Base ethyl epoxide) benzoic acid -4 '-methoxyl group phenyl ester, 4- (6- Methacryloxyhexyls epoxide) benzoic acid Biphenyl Ester, 4- (2- acryloyl-oxyethyls epoxide) benzoic acid -4 '-cyanobiphenyl ester, 4- (2- methacryloxyethyls epoxide) benzene first Sour -4 '-cyanobiphenyl ester, 4- (2- methacryloxyethyls epoxide) benzoic acid -3 ', 4 '-difluoro phenyl ester, 4- (2- methyl Acryloyl-oxyethyl epoxide) naphthol benzoate, 4- -4 '-decyls of acryloxy biphenyl, -4 '-cyano group of 4- acryloxies connection Benzene, 4- (2- acryloyl-oxyethyls epoxide) -4 '-cyanobiphenyl, 4- (2- methacryloxyethyls epoxide) -4 '-methoxy Base the biphenyl,-biphenyl of 4- (2- methacryloxyethyls epoxide) -4 '-(4 "-luorobenzyl epoxide), 4- acryloxies -4 ' - Propylcyclohexyl phenyl, 4- -4 '-butyl of methylacryloyl bis cyclohexane, 4- -4 '-amyl groups of acryloyl group tolans, 4- third Enoyl- -4 '-(3,4- difluorophenyls) bis cyclohexane, 4- (2- acryloyl-oxyethyls) benzoic acid (4- amyl groups phenyl ester), 4- (2- Acryloyl-oxyethyl) benzoic acid (4- (4 '-propylcyclohexyl) phenyl ester) etc..
As commercially available product, LC-242 (BASF AG's system) etc. can be used.In addition, it is possible to use Japanese Unexamined Patent Publication 2007- No. 002208 publication, Japanese Unexamined Patent Publication 2009-173893 publications, Japanese Unexamined Patent Publication 2009-274984 publications, Japanese Unexamined Patent Publication Disclosed in 2010-030979 publications, Japanese Unexamined Patent Publication 2010-031223 publications, Japanese Unexamined Patent Publication 2011-006360 publications etc. Compound etc..
In addition, in addition to above-mentioned exemplified monomer, it is possible to use with multiple acryloyl groups, methylacryloyl, The polyfunctional monomer of the polymerism unsaturated group such as vinyl, pi-allyl.
As such polyfunctional monomer, diacrylate -1,2- butanediol ester, diacrylate -1,3- fourth two can be included The diacrylates such as alcohol ester, diacrylate -1,4- butanediol esters, diacrylic acid pentyl diol ester, diacrylate -1,6-HD ester Alkanediol esters, two (methacrylic acid) -1,2- butanediol esters, two (methacrylic acid) -1,3-BDO esters, two (methyl Acrylic acid) -1,4- butanediol esters, two (methacrylic acid) DOPCPs, two (methacrylic acid) -1,6-HD esters etc. two (methacrylic acid) alkanediol esters, ethylene glycol diacrylate, diacrylate diethylene glycol (DEG) ester, diacrylate triethyleneglycol ester, The allyl methacrylate classes such as diacrylate tetraethylene glycol ester, diacrylate propylene glycol ester, dipropylene glycol diacrylate, two The diacrylate polypropylene glycol esters such as acrylic acid tripropylene glycol ester, the propylene glycol ester of diacrylate four, two (methacrylic acid) second two Alcohol ester, two (methacrylic acid) diethylene glycol (DEG) esters, two (methacrylic acid) triethyleneglycol esters, two (methacrylic acid) tetraethylene glycol esters etc. two (methacrylic acid) polyethylene glycol esters, two (methacrylic acid) propylene glycol esters, two (methacrylic acid) DPG esters, two Two (methacrylic acid) the polypropylene glycol esters such as (methacrylic acid) tripropylene glycol ester, two (methacrylic acid) four propylene glycol ester, The polyethylene glycol such as ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, tetraethylene glycol divinyl ether Divinyl ethers, ethylene glycol diallyl ether, diethylene glycol (DEG) diallyl ether, triethylene glycol diallyl ether, the allyl of tetraethylene glycol two The polyethylene glycol diallyl ethers such as base ether, Ethoxylated bisphenol F the diacrylates, (methacrylic acids of Ethoxylated bisphenol F bis- Ester), ethoxylated bisphenol a diacrylate, Ethoxylated bisphenol A bis- (methacrylate), trimethylolpropane tris propylene Acid esters, trimethylol-propane trimethacrylate, ethoxylated trimethylolpropane triacrylate, the hydroxyl first of ethoxylation three Base propane trimethyl acrylic ester, propoxylation trimethylolpropane trimethacrylate, propoxylation trimethylolpropane tris first Base acrylate, ethoxylation isocyanuric acid triacrylate, ethoxylated glycerol triacrylate, propoxylated glycerol 3 third Olefin(e) acid ester, ethoxylation tetramethylol methane tetraacrylate, ethoxylation two (trimethylolpropane) tetraacrylate, ethoxylation Dipentaerythritol acrylate etc..
The (co) polymerization of the polymerizable compound and other copolymerizable monomers for using as needed of the present invention etc. can Carried out in the presence of appropriate polymerization initiator.As the use ratio of polymerization initiator, can with relative to above-mentioned polymerism group The mixing proportion of polymerizable compound in compound is identical.
It is the copolymer of the polymerizable compound of the present invention monomers copolymerizable with others in the macromolecule of the present invention In the case of, the content of polymerizable compound unit of the invention is not particularly limited, but relative to whole Component units preferably 50 weights Measure more than %, more preferably more than 70 weight %.If in such scope, high molecular glass transition temperature (Tg) is high, High film hardness is can obtain, so it is preferred that.
The macromolecule of above-mentioned (1) more specifically can be waited by the following method suitably to be prepared：(A) draw in appropriate polymerization Send out in the presence of agent, the (co) polymerization of above-mentioned polymerizable compound and the other copolymerizable monomers used as needed etc. is existed Carried out in appropriate organic solvent after polymerisation, the macromolecule as target is separated, by obtained macromolecule dissolution in appropriate Organic solvent in so as to preparing solution, after solution coating dried coating film obtained from appropriate substrate, according to need Heated the method obtained from；(B) by above-mentioned polymerizable compound and use as needed it is other copolymerizable Solution is coated with by known rubbing method on substrate obtained from monomer etc. is dissolved in organic solvent together with polymerization initiator Afterwards, desolventizing is carried out, then by heating or irradiating active energy beam so as to carry out method of polymerisation etc..
As used polymerization initiator, it can include and drawing exemplified by the composition as above-mentioned polymerizable composition, polymerizable composition Send out agent identical initiator.
As organic solvent used in the polymerisation of above-mentioned (A), if inert organic solvent, then without special limit System.For example, the aromatic hydrocarbons such as toluene, dimethylbenzene, mesitylene can be included, the ketone, acetic acid such as cyclohexanone, cyclopentanone, MEK The acetates such as butyl ester, amyl acetate, the halogenated hydrocarbon, cyclopentyl-methyl ether, tetrahydrochysene furan such as chloroform, dichloromethane, dichloroethanes Mutter, the ethers such as oxinane etc..Wherein, from the viewpoint of operability is excellent, preferably boiling point is 60~250 DEG C of solvent, more It is preferred that boiling point is 60~150 DEG C of solvent.
The organic solvent used in high molecular organic solvent and (B) method is dissolved as being used in the method for (A), The ketones solvents such as acetone, MEK, methyl iso-butyl ketone (MIBK), cyclopentanone, cyclohexanone, butyl acetate, amyl acetate etc. can be included Esters solvent, the halogenated hydrocarbon solvent, tetrahydrofuran, oxinane, 1,2- dimethoxys such as dichloromethane, chloroform, dichloroethanes The ether solvents such as ethane, the dioxane of Isosorbide-5-Nitrae-, cyclopentyl-methyl ether, DOX, DMF, N, N- diformazans Aprotic polar solvents such as yl acetamide, dimethyl sulfoxide (DMSO), gamma-butyrolacton, 1-METHYLPYRROLIDONE etc..Wherein, from operation From the viewpoint of easily, the boiling point of preferred solvent is 60~200 DEG C of solvent.These solvents can be used alone or by two or more Combination is used.
It is no matter organic and inorganic as used substrate, the substrate of known usual material can be used.For example, as having Machine material, can include polycyclic alkene [such as Zeonex, Zeonor (registration mark, Zeon Corporation systems), Arton (registration mark；JSR company systems), and Apel (registration mark, Mitsui Chemicals society system)], polyethylene terephthalate, poly- carbon Acid esters, polyimides, polyamide, polymethyl methacrylate, polystyrene, polyvinyl chloride, polytetrafluoroethylene (PTFE), cellulose, three Cellulose acetate, polyether sulfone etc.；Silicon, glass, calcite etc. can be included as inorganic material, wherein it is preferred that organic material.
In addition, used substrate can be the substrate or layered product of individual layer.
As substrate, preferred organic material further preferably the organic material is made the resin film of film.
High molecular solution coating will be polymerize instead in the method for substrate, in the method for (B) as in the method for (A) The method that solution application is coated on substrate, can be used known method, can for example include curtain coating processes, extrusion coating methods, Print roll coating method, method of spin coating, Dipcoat method, scraper rubbing method, spraying coating method, slope flow coat cloth method (slide Coating), printing rubbing method etc..
(2) by macromolecule obtained from the polymerizable composition, polymerizable composition polymerization of the present invention
By the way that the polymerizable composition, polymerizable composition of the present invention is polymerize, the macromolecule of the present invention can be readily derived.In the present invention, From being more effectively carried out from the viewpoint of polymerisation, preferably use and gather containing polymerization initiator as described above, particularly light Close the polymerizable composition, polymerizable composition of initiator.
Specifically, preferably by the method for above-mentioned (B), polymerizable composition, polymerizable composition that will be of the invention is coated on substrate simultaneously It is polymerize, obtains the macromolecule of the present invention.As used substrate, the preparation of aftermentioned optically anisotropic body can be included Middle substrate used etc..
As the method being coated on the polymerizable composition, polymerizable composition of the present invention on substrate, it can include and scrape rod coating, rotation painting Known in cloth, print roll coating, gravure, spraying coating, die head coating, bell-type coating (cap coating), infusion process etc. Usual rubbing method.Now, in order to improve coating, it can add known usual organic into the polymerizable composition, polymerizable composition of the present invention Solvent.In this case, it is preferably dry by spontaneously drying, heating after the polymerizable composition, polymerizable composition of the present invention is coated on substrate It is dry, be dried under reduced pressure, vacuum drying under reduced pressure etc. removes organic solvent.
As by the method for the polymerizable compound of the present invention or polymerizable composition, polymerizable composition polymerization, it can include and irradiate active energy Method, thermal polymerization of ray etc. are measured, the method for active energy beam is irradiated due to that need not heat, is reacted at room temperature, So it is preferred that.Wherein, due to easy to operate, it is advantageous to the method for the light such as irradiation ultraviolet radiation.
Temperature during irradiation is preferably set to less than 30 DEG C.Photo-irradiation intensity is usually 1W/m2~10kW/m2Scope, preferably For 5W/m2~2kW/m2Scope.
Can be from strippable substrate by macromolecule obtained from the polymerizable compound of the present invention or polymerizable composition, polymerizable composition polymerization It is used alone, or do not used directly as organic material of optical film etc. from strippable substrate.
As above the high molecular number-average molecular weight of the invention obtained is preferably 500~500,000, more preferably 5, 000~300,000.If the number-average molecular weight is in such scope, high film hardness, operational also excellent, institute can obtain With preferred.On high molecular number-average molecular weight, can using monodispersed polystyrene as standard sample, using tetrahydrofuran as Eluent is determined by gel permeation chromatography (GPC).
Speculate that the polymer crosslinking point of the present invention equably exists in intramolecular, cross-linking efficiency is high, hardness is excellent.
According to the macromolecule of the present invention, it inexpensive can obtain that uniform polarised light can be carried out in wide wave-length coverage Conversion in the gratifying optical film of aspect of performance.
4) optically anisotropic body
The optically anisotropic body of the present invention is used as constituent material using the macromolecule of the present invention.
The optically anisotropic body of the present invention can for example be obtained by the following method：Alignment films are formed on substrate, at this The liquid crystal layer being made up of the macromolecule of the present invention is further formed in alignment films.
Alignment films are to be limited to a direction in order to which organic semiconductor compound is orientated in face and formed in substrate Surface.
Alignment films can be obtained by the following method：Polyimides, polyvinyl alcohol, polyester, polyene third will be contained on substrate The solution (orientation film composition) of the polymer such as glycolylate (polyallylate), polyamidoimide, PEI is applied Cloth film-like, is dried, and processing etc. is then ground in a direction.
The thickness of alignment films is preferably 0.001~5 μm, more preferably 0.001~1 μm.
In the present invention, milled processed can be implemented to alignment films or substrate.The method of milled processed is without specifically limited, but example It can such as include with being wound with the roller of the cloth being made up of natural fibers such as nylon synthetic fibers, cottons or felt in a certain direction The method of friction orientation film.It is cleaning to make the surface of alignment films in order to remove the micro mist produced in milled processed (foreign matter) State, alignment films are cleaned preferably after milled processed by isopropanol etc..
In addition, in addition to the method for being ground processing, the side of polarized UV rays is irradiated by the surface to alignment films Method, can also make it have the function that the orientation in face is limited to a direction.
In the present invention, the method for the liquid crystal layer being made up of as being formed in alignment films the macromolecule of the present invention, can be arranged Enumerate and the method identical method described in the high score subitem in the invention described above.
Due to the present invention optically anisotropic body using the present invention macromolecule be used as constituent material, it is possible to low cost Prepare, reflecting brightness is low, and can carry out uniform polarised light conversion in wide wave-length coverage, also excellent in aspect of performance It is different.
As the optically anisotropic body of the present invention, polarizer, alignment films used for liquid crystal display element, polarisation can be included Plate, visual angle expand plate, colour filter, low pass filter, optical polarization prism, various optical filters etc..
5) carbonyls
The carbonyls of the present invention is the compound represented with above-mentioned formula (4).
As described above, the carbonyls (4) of the present invention can be suitable as the preparation of the polymerizable compound (I) of the present invention Intermediate.It is illustrated in the details of the preparation method of carbonyls (4) such as the polymerizable compound of above-mentioned 1).
6) method of the preparation method of polymerizable compound and the preparing raw material as polymerizable compound
" preparation method of polymerizable compound " of the present invention is the preparation method of the polymerizable compound (I) of the present invention, Characterized in that, reacting hydrazine compound of the carbonyls (4) of the present invention with being represented with above-mentioned formula (3).Preparation method It is illustrated in details such as above-mentioned 1) polymerizable compound.
According to the preparation method of the polymerizable compound of the present invention, the polymerism of the present invention can effectively and be easily prepared Compound (I).
" method for being used as the preparing raw material of polymerizable compound " of the present invention is the carbonyls (4) using the present invention It is used as the method for the preparing raw material of polymerizable compound (I).Specifically, as illustrated in 1) polymerizable compound.
By using the carbonyls (4) of the present invention as preparing raw material, the present invention can be easily prepared in high yield Polymerizable compound (I).
Embodiment
The present invention is further explained by the following examples.But, the present invention is not because of following examples It is any way limited.
The synthesis of (embodiment 1) compound 1
[changing 38]
Step 1：The synthesis of intermediate A
[changing 39]
17.98g (104.42mmol) anti-form-1,4- are added into the three neck reactors for possess thermometer in nitrogen stream Cyclohexyl dicarboxylic acid and 180ml tetrahydrofuran (THF).6.58g (57.43mmol) mesyl chloride is added thereto, will be reacted Device is impregnated in water-bath and makes temperature in reaction solution be 20 DEG C.Then, temperature remains 20~30 DEG C same in by reaction solution When, with the triethylamine that 6.34g (62.65mmol) is added dropwise for 10 minutes.It is after completion of dropwise addition, all the elements thing is further in 25 DEG C Stirring 2 hours.
0.64g (5.22mmol) 4- (dimethylamino) pyridines and 13.80g is added into obtained reaction solution Reactor, is impregnated in by 4- (6- acryloxies-hex- 1- bases epoxide) phenol (DKSH company systems) of (52.21mmol) again It is 15 DEG C to make temperature in reaction solution in water-bath.While temperature remains 20~30 DEG C in by reaction solution, with 10 minutes to 6.34g (62.65mmol) triethylamine is wherein added dropwise, it is after completion of dropwise addition, all the elements thing is small in 25 DEG C of further stirrings 2 When.After the completion of reaction, 1000ml distilled water and 100ml saturated aqueous common salt are added into reaction solution, with 400ml acetic acid Ethyl ester is extracted 2 times.Collected organic layer, after anhydrous sodium sulfate drying, filters out sodium sulphate.Removed with rotary evaporator from filtrate evaporation Go after solvent, obtained residue is passed through into silica gel column chromatography (THF:Toluene=1:9 (volumetric ratio, it is same as below.)) purifying, Thus 14.11g intermediate A (yield is obtained as white solid：65%).
The structure of object passes through1H-NMR is identified.
1H-NMR(500MHz,DMSO-d6,TMS,δppm)：12.12 (s, 1H), 6.99 (d, 2H, J=9.0Hz), 6.92 (d, 2H, J=9.0Hz), 6.32 (dd, 1H, J=1.5Hz, 17.5Hz), 6.17 (dd, 1H, J=10.0Hz, 17.5Hz), 5.93 (dd, 1H, J=1.5Hz, 10.0Hz), 4.11 (t, 2H, J=6.5Hz), 3.94 (t, 2H, J=6.5Hz), 2.48-2.56 (m, 1H)、2.18-2.26(m.1H)、2.04-2.10(m,2H)、1.93-2.00(m,2H)、1.59-1.75(m,4H)、1.35-1.52 (m,8H)。
Step 2：The synthesis of intermediate B
[changing 40]
In nitrogen stream into the three neck reactors for possess thermometer add 4.00g (9.56mmol) in above-mentioned steps 1 The intermediate A of middle synthesis and 60ml THF, are made uniform solution.1.12g (9.78mmol) methylsulfonyl is added thereto Chlorine, reactor is impregnated in water-bath and makes temperature in reaction solution be 20 DEG C.Then, in by reaction solution temperature remain 20~ While 30 DEG C, with the triethylamine that 1.01g (9.99mmol) is added dropwise for 5 minutes, after completion of dropwise addition, by all the elements thing in 25 DEG C Further stir 2 hours.0.11g (0.87mmol) 4- (dimethylamino) pyridines and 0.60g is added into obtained reaction solution Reactor, is impregnated in water-bath and makes temperature in reaction solution be 15 DEG C by 2, the 5- 4-dihydroxy benzaldehydes of (4.35mmol) again. While temperature remains 20~30 DEG C in by reaction solution, 1.10g (10.87mmol) three second were added dropwise thereto with 5 minutes Amine, after completion of dropwise addition, all the elements thing is further stirred 2 hours in 25 DEG C.After the completion of reaction, added into reaction solution 400ml distilled water and 50ml saturated aqueous common salt, with 750ml ethyl acetate extraction 2 times.Collected organic layer, uses anhydrous sulphur After sour sodium is dried, sodium sulphate is filtered out.With rotary evaporator after filtrate evaporation of solvent, obtained residue is dissolved in In 100ml THF.500ml methanol is added into the solution and crystallization is separated out, the crystallization that leaching is separated out.By obtained crystallization After being cleaned with methanol, vacuum drying obtains 2.51g intermediate B (yield as white solid：62%).
The structure of object passes through1H-NMR is identified.
1H-NMR(500MHz,DMSO-d6,TMS,δppm)：10.02 (s, 1H), 7.67 (d, 1H, J=3.0Hz), 7.55 (dd, 1H, J=3.0Hz, 8.5Hz), 7.38 (d, 1H, J=8.5Hz), 6.99-7.04 (m, 4H), 6.91-6.96 (m, 4H), 6.32 (dd, 2H, J=1.5Hz, 17.5Hz), 6.17 (dd, 2H, J=10.0Hz, 17.5Hz), 5.93 (dd, 2H, J=1.5Hz, 10.0Hz), 4.11 (t, 4H, J=6.5Hz), 3.95 (t, 4H, J=6.5Hz), 2.56-2.81 (m, 4H), 2.10-2.26 (m, 8H)、1.50-1.76(m,16H)、1.33-1.49(m,8H)。
Step 3：The synthesis of compound 1
In nitrogen stream into the three neck reactors for possess thermometer add 2.30g (2.45mmol) in above-mentioned steps 2 The intermediate B of middle synthesis and 25ml THF, are made uniform solution, and 0.49ml (0.25mmol) concentrated hydrochloric acid is added thereto. The 5ml THF solutions of 0.40g (2.45mmol) 2- hydrazinobenzothiazoles were added dropwise into the solution with 15 minutes, in completion of dropwise addition Afterwards, all the elements thing is further stirred 1 hour in 25 DEG C.After the completion of reaction, reaction solution is put into 400ml methanol simultaneously The solid that leaching is separated out.The solid of leaching is dried with vacuum drier, 2.4g compound 1 is obtained as faint yellow solid (yield：90%).
The structure of object passes through1H-NMR is identified.
1H-NMR(500MHz,DMSO-d6,TMS,δppm)：12.63 (s, 1H), 8.10 (s, 1H), 7.80 (d, 1H, J= 5.0Hz), 7.60 (d, 1H, J=3.0Hz), 7.48 (s, 1H), 7.21-7.35 (m, 3H), 7.14 (t, 1H, J=7.5Hz), 6.98-7.05 (m, 4H), 6.91-6.97 (m, 4H), 6.32 (dd, 2H, J=1.5Hz, 17.5Hz), 6.18 (dd, 2H, J= 10.0Hz, 17.5Hz), 5.93 (dd, 2H, J=1.5Hz, 10.0Hz), 4.12 (t, 4H, J=6.5Hz), 3.95 (t, 4H, J= 6.5Hz)、2.56-2.83(m,4H)、2.11-2.30(m,8H)、1.52-1.80(m,16H)、1.33-1.49(m,8H)。
The synthesis of (embodiment 2) compound 2
[changing 41]
Step 1：Intermediate C synthesis
[changing 42]
9.00g (70.01mmol) 3- amino -2- chlorine is added into the three neck reactors for possess thermometer in nitrogen stream The concentrated hydrochloric acid of pyridine and 90ml, is made uniform solution.10.21g (105.01mmol) potassium rhodanide is added thereto, by institute There is content to be stirred 4 hours in 100 DEG C.After the completion of reaction, reaction solution is cooled to 20 DEG C, adds 90ml water.Ice-cold It is lower will in reactant mixture input 300ml saturated sodium bicarbonate aqueous solution, further input powdered sodium carbonate and by solution PH be adjusted to 8, separate out crystallization.The solid separated out is filtered, after being cleaned with distilled water, is dried with vacuum drier, as yellowish Color solid obtains 8.74g intermediate C (yields：83%).
The structure of object passes through1H-NMR is identified.
1H-NMR(500MHz,DMSO-d6,TMS,δppm)：8.11 (dd, 1H, J=1.5Hz, 5.0Hz), 7.82 (s, 2H), 7.63 (dd, 1H, J=1.5Hz, 8.0Hz), 7.25 (dd, 1H, J=5.0Hz, 8.0Hz).
Step 2：Intermediate D synthesis
[changing 43]
CH3CH2CH2CH2CH2CH2-NHNH2
Intermediate D
182.0g (3635mmol) hydrazine monohydrate is added into the three neck reactors for possess thermometer, in nitrogen stream It is heated to 40 DEG C.60.0g (363.5mmol) hexyl bromide 1 bromohexane and 60ml second was added dropwise thereto with 4 hours using dropping funel The mixed solution of alcohol.After completion of dropwise addition, all the elements thing is stirred 1 hour in 40 DEG C.Reaction solution is cooled to after 25 DEG C, plus Enter 200ml distilled water, extracted 2 times with 300ml chloroform.Collected organic layer, after anhydrous sodium sulfate drying, filters out sulfuric acid Sodium.Filtrate is concentrated with rotary evaporator, thus concentrate vacuum distillation is obtained in 10.44g as colourless transparent liquid Mesosome D (vacuums：3.0kPa, boiling point：90 DEG C) (yield：25%).
The structure of object passes through1H-NMR is identified.
1H-NMR(500MHz,DMSO-d6,TMS,δppm)：3.02 (s, 3H), 2.76 (t, 2H, J=7.0Hz), 1.44- 1.53 (m, 2H), 1.24-1.37 (m, 6H), 0.89 (t, 3H, J=7.0Hz).
Step 3：The synthesis of intermediate E
[changing 44]
In nitrogen stream into the three neck reactors for possess thermometer add 2.70g (17.86mmol) in above-mentioned steps 1 Intermediate C, 10.38g (89.29mmol) of middle synthesis intermediate D, 1.49ml for synthesizing in step 2 above The concentrated hydrochloric acid of (17.86mmol) and 25ml ethylene glycol, are made uniform solution, and the solution is stirred 20 hours in 140 DEG C. After reaction terminates, reaction solution is cooled to 20 DEG C, 300ml distilled water and 50ml saturated aqueous common salt are added, with 500ml vinegar Acetoacetic ester is extracted.After organic layer anhydrous sodium sulfate drying, sodium sulphate is filtered out., will after with rotary evaporator, filtrate is concentrated Concentrate passes through silica gel column chromatography (THF:Toluene=1:9) purify, 1.33g intermediate is thus obtained as faint yellow solid E (yields：30%).
The structure of object passes through1H-NMR is identified.
1H-NMR(500MHz,DMSO-d6,TMS,δppm)：8.07 (dd, 1H, J=1.5Hz, 5.0Hz), 7.62 (dd, 1H, J=1.5Hz, 8.0Hz), 7.22 (dd, 1H, J=5.0Hz, 8.0Hz), 5.46 (s, 2H), 3.70 (t, 2H, J=7.0Hz), 1.64-1.73 (m, 2H), 1.22-1.35 (m, 6H), 0.86 (t, 3H, J=7.0Hz).
Step 4：The synthesis of compound 2
Add into the three neck reactors for possess thermometer in nitrogen stream 1.20g (1.28mmol) in embodiment 1 The intermediate B and 30ml THF synthesized in step 2, is made uniform solution.0.26ml (0.26mmol) 1N is added thereto Hydrochloric acid, the 5ml THF with the intermediate E synthesized in above-mentioned synthesis step 3 that 0.48g (1.92mmol) is added dropwise for 15 minutes are molten Liquid.After completion of dropwise addition, all the elements thing is further stirred 5 hours in 25 DEG C.Reaction solution is put into 250ml methanol In, the solid that leaching is separated out.Obtained solid is passed through into silica gel column chromatography (chloroform:THF=97:3) purify, thus as light Yellow solid obtains the 1.25g (yield of compound 2：84%).
The structure of object passes through1H-NMR is identified.
1H-NMR(500MHz,DMSO-d6,TMS,δppm)：8.30 (dd, 1H, J=1.5Hz, 5.0Hz), 7.96 (dd, 1H, J=1.5Hz, 8.0Hz), 7.89 (s, 1H), 7.63 (d, 1H, J=3.0Hz), 7.39 (dd, 1H, J=5.0Hz, 8.0Hz), 7.32 (d, 1H, J=8.5Hz), 7.27 (dd, 1H, J=3.0Hz, 8.5Hz), 6.98-7.04 (m, 4H), 6.91-6.97 (m, 4H), 6.32 (dd, 2H, J=1.5Hz, 17.5Hz), 6.17 (dd, 2H, J=10.0Hz, 17.5Hz), 5.93 (dd, 2H, J= 1.5Hz, 10.0Hz), 4.35 (t, 2H, J=7.0Hz), 4.11 (t, 4H, J=6.5Hz), 3.95 (t, 4H, J=6.5Hz), 2.56-2.84(m,4H)、2.11-2.30(m,8H)、1.52-1.75(m,18H)、1.22-1.49(m,14H)、0.85(t,3H,J =7.0Hz).
The synthesis of (embodiment 3) compound 3
[changing 45]
Step 1：Intermediate F synthesis
[changing 46]
20.0g (125mmol) 1,4- dihydroxy naphthlenes are added into the four neck reactors for possess thermometer in nitrogen stream With 200ml DMF (DMF), uniform solution is made.51.8g (375mmol) carbonic acid is added thereto The iodomethane of potassium, 19.4ml (312mmol), all the elements thing is stirred 20 hours in 25 DEG C.After the completion of reaction, diatomite is used Filtering reacting liquid.In the water that filtrate is put into 500ml, with 500ml ethyl acetate extraction.By ethyl acetate layer anhydrous slufuric acid Sodium is dried.Filter out after sodium sulphate, ethyl acetate is distilled off from filtrate decompression with rotary evaporator, white solid is obtained.Should White solid is recrystallized by n-hexane (125ml), and 20.3g intermediate F (yields are thus obtained as clear crystal： 86.3%).
The structure of object passes through1H-NMR is identified.
1H-NMR(500MHz,CDCl3,TMS,δppm)：8.19-8.22(m,2H)、7.52-7.48(m,2H)、6.69(s, 2H)、3.95(s,6H)。
Step 2：Intermediate G synthesis
[changing 47]
In nitrogen stream into the four neck reactors for possess thermometer add 15.0g (79.7mmol) in above-mentioned steps 1 The intermediate F and 100ml of middle synthesis dichloromethane, are made uniform solution, are cooled to 0 DEG C.It is added dropwise into the solution 91.7ml (91.7mmol) titanium tetrachloride (1.0M dichloromethane solutions) and 8.11ml (91.7mmol) dichloromethyl methyl Ether, is stirred 1 hour in 0 DEG C.After the completion of reaction, reaction solution is put into 300ml frozen water, extracted with 500ml ethyl acetate Take.Ethyl acetate layer is dried with anhydrous magnesium sulfate, magnesium sulfate is filtered out.Acetic acid is distilled off from filtrate decompression with rotary evaporator Ethyl ester, obtains white solid.The white solid is recrystallized by 260ml n-hexane, thus obtained as colourless crystallization 16.6g intermediate G (yields：96.4%).
The structure of object passes through1H-NMR is identified.
1H-NMR(500MHz,CDCl3,TMS,δppm)：10.58(s,1H)、8.28-8.31(m,1H)、8.20-8.22(m, 1H)、7.61-7.67(m,2H)、7.13(s,1H)、4.10(s,3H)、4.03(s,3H)。
Step 3：Intermediate H synthesis
[changing 48]
In nitrogen stream into the four neck reactors for possess thermometer add 16.6g (76.8mmol) in above-mentioned steps 2 The intermediate G and 100ml of middle synthesis dichloromethane, are made uniform solution, are cooled to -40 DEG C.230ml is added dropwise thereto After the Boron tribromide (17% dichloromethane solution) of (230mmol), 25 DEG C are warming up to, all the elements thing is stirred 2 hours.Anti- After should terminating, reaction solution is put into 500ml frozen water, extracted with 500ml dichloromethane.By dichloromethane layer with anhydrous Magnesium sulfate is dried, and filters out magnesium sulfate.Dichloromethane is distilled off from filtrate decompression with rotary evaporator, yellow solid is obtained.Will The yellow solid passes through silica gel column chromatography (n-hexane:Ethyl acetate=70:30) purify, 12.7g is obtained as yellow solid Intermediate H (yields：87.9%).
The structure of object passes through1H-NMR is identified.
1H-NMR(500MHz,CDCl3,TMS,δppm)：12.31 (s, 1H), 9.88 (s, 1H), 8.45 (d, 1H, J= 8.5Hz), 8.16 (d, 1H, J=8.5Hz), 7.72 (dd, 1H, J=7.8Hz, 8.5Hz), 7.61 (dd, 1H, J=7.8Hz, 8.5Hz)、6.83(s,1H)、5.17(s,1H)。
Step 4：The synthesis of intermediate compound I
[changing 49]
Add into the three neck reactors for possess thermometer in nitrogen stream 3.19g (7.61mmol) in embodiment 1 The intermediate A and 50ml THF synthesized in step 1, is made uniform solution.0.91g (7.93mmol) first is added thereto Sulfonic acid chloride, reactor is impregnated in water-bath and makes temperature in reaction solution be 20 DEG C.Then, temperature is remained in by reaction solution While 20~30 DEG C, with the triethylamine that 0.80g (7.93mmol) is added dropwise for 5 minutes.After completion of dropwise addition, by all the elements thing in 25 DEG C are stirred 2 hours.0.08g (0.63mmol) 4- (dimethylamino) pyridine, 0.60g is added into obtained reactant mixture Reactor, is impregnated in water-bath and makes the temperature in reaction solution be by the intermediate H synthesized in step 3 of (3.17mmol) again 15℃.While temperature remains 20~30 DEG C in by reaction solution, it was added dropwise 0.80g's (7.93mmol) thereto with 5 minutes Triethylamine, after completion of dropwise addition, all the elements thing is further stirred 2 hours in 25 DEG C.150ml steaming is added into reaction solution The saturated aqueous common salt of distilled water and 50ml, with 300ml ethyl acetate extraction 2 times.Collected organic layer, uses anhydrous sodium sulfate drying Afterwards, sodium sulphate is filtered out.Filtrate is concentrated with rotary evaporator, by obtained solid dissolving in 100ml THF.To the solution Middle addition 500ml methanol and separate out crystallization, leaching separate out crystallization.After obtained crystallization is cleaned with methanol, vacuum drying, 1.82g intermediate compound I (yield is obtained as pale solid：58%).
The structure of object passes through1H-NMR is identified.
1H-NMR(500MHz,DMSO-d6,TMS,δppm)：10.22 (s, 1H), 8.11 (d, 1H, J=8.5Hz), 7.99 (d, 1H, J=8.5Hz), 7.76-7.91 (m, 2H), 7.71 (s, 1H), 7.01-7.07 (m, 4H), 6.91-6.98 (m, 4H), 6.32 (dd, 2H, J=1.5Hz, 17.5Hz), 6.18 (dd, 2H, J=10.0Hz, 17.5Hz), 5.94 (dd, 2H, J=1.5Hz, 10.0Hz), 4.12 (t, 4H, J=6.5Hz), 3.96 (t, 4H, J=6.5Hz), 3.02-3.12 (m, 1H), 2.86-2.97 (m, 1H)、2.60-2.74(m,2H)、2.28-2.43(m,4H)、2.14-2.27(m,4H)、1.54-1.86(m,16H)、1.30- 1.53(m,8H)。
Step 5：The synthesis of compound 3
1.67g (1.69mmol) conjunction in step 4 is added into the three neck reactors for possess thermometer in nitrogen stream Into intermediate compound I and 30ml THF, uniform solution is made.0.34ml (0.34mmol) 1N hydrochloric acid is added thereto, with 30 The 5ml THF solutions of 0.85g (3.38mmol) intermediate E synthesized in the step 3 of embodiment 2 are added dropwise in minute, are being added dropwise After end, all the elements thing is stirred 5 hours in 25 DEG C.Reaction solution is put into 250ml methanol, what leaching was separated out consolidates Body.The solid of leaching is passed through into silica gel column chromatography (chloroform:THF=97:3) purify, thus obtained as faint yellow solid 1.61g (the yield of compound 3：78%).
The structure of object passes through1H-NMR is identified.
1H-NMR(500MHz,DMSO-d6,TMS,δppm)：8.31 (dd, 1H, J=1.5Hz, 5.0Hz), 7.94-7.99 (m, 2H), 7.88-7.94 (m, 2H), 7.78 (s, 1H), 7.69-7.76 (m, 2H), 7.40 (dd, 1H, J=5.0Hz, 8.0Hz), 6.99-7.08 (m, 4H), 6.90-6.98 (m, 4H), 6.32 (dd, 2H, J=1.5Hz, 17.5Hz), 6.18 (dd, 2H, J= 10.0Hz, 17.5Hz), 5.94 (dd, 2H, J=1.5Hz, 10.0Hz), 4.40 (t, 2H, J=7.0Hz), 4.12 (t, 4H, J= 6.5Hz), 3.96 (t, 2H, J=6.5Hz), 3.95 (t, 2H, J=6.5Hz), 2.89-3.12 (m, 2H), 2.61-2.75 (m, 2H)、2.30-2.42(m,4H)、2.15-2.28(m,4H)、1.55-1.85(m,18H)、1.19-1.52(m,14H)、0.86(t, 3H, J=7.0Hz).
The synthesis of (embodiment 4) compound 4
[changing 50]
Step 1：Intermediate J synthesis
[changing 51]
2.00g (12.1mmol) 2- diazanyl benzo thiophenes are added into the four neck reactors for possess thermometer in nitrogen stream The DMF of azoles and 20ml, is made uniform solution.8.36g (60.5mmol) potassium carbonate, 3.08g is added into the solution The 1- iodohexanes of (14.5mmol), all the elements thing is stirred 7 hours in 50 DEG C.After the completion of reaction, reaction solution is cooled to 20 DEG C, reaction solution is put into 200ml water, with 300ml ethyl acetate extraction.By ethyl acetate layer anhydrous sodium sulfate Dry, filter out sodium sulphate.Ethyl acetate is distilled off from filtrate decompression with rotary evaporator, yellow solid is obtained.By the yellow Solid passes through silica gel column chromatography (hexane:Ethyl acetate=75:25) purify, 2.10g intermediate J is obtained as white solid (yield：69.6%).
The structure of object passes through1H-NMR is identified.
1H-NMR(500MHz,CDCl3,TMS,δppm)：7.60 (dd, 1H, J=1.0Hz, 8.0Hz), 7.53 (dd, 1H, J =1.0Hz, 8.0Hz), 7.27 (ddd, 1H, J=1.0Hz, 8.0Hz, 8.0Hz), 7.06 (ddd, 1H, J=1.0Hz, 8.0Hz, 8.0Hz), 4.22 (s, 2H), 3.74 (t, 2H, J=7.5Hz), 1.69-1.76 (m, 2H), 1.29-1.42 (m, 6H), 0.89 (t, 3H, J=7.0Hz).
Step 2：The synthesis of compound 4
In nitrogen stream into the four neck reactors for possess thermometer add 697mg (2.37mmol) in above-mentioned steps 1 Intermediate J, 2.00g (2.13mmol) of the middle synthesis intermediate B synthesized in embodiment 1,3ml ethanol and 20ml THF, is made uniform solution.55.1mg (0.24mmol) (±) -10- camphorsulfonic acids are added into the solution, will be all interior It is tolerant to be stirred 5 hours in 40 DEG C.After the completion of reaction, reaction solution is put into 150ml water, with 300ml ethyl acetate Extraction.By ethyl acetate layer anhydrous sodium sulfate drying, sodium sulphate is filtered out.Vinegar is distilled off from filtrate decompression with rotary evaporator Acetoacetic ester, obtains white solid.The white solid is passed through into silica gel column chromatography (toluene:Ethyl acetate=90:10) purify, make 2.24g (the yield of compound 4 is obtained for white solid：86.4%).
The structure of object passes through1H-NMR is identified.
H-NMR(400MHz,CDCl3,TMS,δppm)：7.75 (d, 1H, J=2.5Hz), 7.67-7.70 (m, 3H), 7.34 (ddd, 1H, J=1.0Hz, 7.0Hz, 7.5Hz), 7.17 (ddd, 1H, J=1.0Hz, 7.5Hz, 7.5Hz), 7.12 (d, 1H, J= 9.0Hz), 7.10 (dd, 1H, J=2.5Hz, 9.0Hz), 6.99 (d, 2H, J=9.0Hz), 6.98 (d, 2H, J=9.0Hz), 6.88 (d, 4H, J=9.0Hz), 6.40 (dd, 2H, J=1.5Hz, 17.0Hz), 6.13 (dd, 2H, J=10.5Hz, 17.5Hz), (5.82 dd, 2H, J=1.5Hz, 10.5Hz), 4.30 (t, 2H, J=8.0Hz), 4.18 (t, 4H, J=6.5Hz), 3.95 (t, 4H, J=6.5Hz), 2.58-2.70 (m, 4H), 2.31-2.35 (m, 8H), 1.66-1.82 (m, 18H), 1.31-1.54 (m, 14H), 0.90 (t, 3H, J=7.0Hz).
The synthesis of (embodiment 5) compound 5
[changing 52]
Step 1：Intermediate K synthesis
[changing 53]
1.50g (6.48mmol) 2- (methyl mercapto) naphthalene is added into the four neck reactors for possess thermometer in nitrogen stream And [1,2d] thiazole and 15ml dichloromethane, uniform solution is made.In 0 DEG C 3.52g is added into the solution (about aqueous 30%) stirs all the elements thing 8 hours in 25 DEG C to the 3- chloroperoxybenzoic acids of (14.3mmol).Terminate in reaction Afterwards, reaction solution is put into 100ml saturated sodium bicarbonate aqueous solution, extracted with 200ml dichloromethane.By dichloromethane Layer is dried with anhydrous magnesium sulfate, filters out magnesium sulfate.Dichloromethane is distilled off from filtrate decompression with rotary evaporator, white is obtained Solid.The white solid is passed through into silica gel column chromatography (toluene:Ethyl acetate=90:10) purify, obtained as white solid 1.49g intermediate K (yields：74.6%).
The structure of object passes through1H-NMR and13C-NMR is identified.
1H-NMR(400MHz,CDCl3,TMS,δppm)：8.84 (d, 1H, J=7.6Hz), 8.00 (d, 1H, J=8.0Hz), 7.99 (d, 1H, J=9.2Hz), 7.95 (d, 1H, J=9.2Hz), 7.75 (dd, 1H, J=7.6Hz, 8.0Hz), 7.68 (dd, 1H, J=7.6Hz, 7.6Hz), 3.48 (s, 3H)
13C-NMR(100MHz,CDCl3,TMS,δppm)：164.6、149.7、134.7、132.3、129.5、129.2、 128.4、128.1、127.5、124.0、118.7、42.8。
Step 2：Intermediate L synthesis
[changing 54]
In nitrogen stream into the four neck reactors for possess thermometer add 1.49g (4.83mmol) in above-mentioned steps 1 Intermediate K, 1.2ml (24.2mmol) hydrazine monohydrate, 10ml 1- propyl alcohol and the 5ml THF of middle synthesis, are made uniform Solution, all the elements thing is stirred 4 hours in 80 DEG C.After the completion of reaction, reaction solution is cooled to 20 DEG C, adds 100ml's Water, the solid that leaching is separated out.After the solid of leaching is cleaned with water, dried, obtained as faint yellow solid with vacuum drier 993mg intermediate L (yields：95.5%).
The structure of object passes through1H-NMR is identified.
1H-NMR(500MHz,DMSO-d6,TMS,δppm)：9.20 (s, 1H), 8.34 (d, 1H, J=8.0Hz), 7.90 (d, 1H, J=8.0Hz), 7.83 (d, 1H, J=8.5Hz), 7.53 (d, 1H, J=8.5Hz), 7.51 (dd, 1H, J=7.5Hz, 8.0Hz), 7.46 (dd, 1H, J=7.5Hz, 8.0Hz), 5.12 (s, 2H).
Step 3：Intermediate M synthesis
[changing 55]
In nitrogen stream 993g (4.61mmol) is added into the four neck reactors for possess thermometer in step 2 above The intermediate L and 10ml of synthesis DMF, are made uniform solution.3.00g (9.22mmol) cesium carbonate is added into the solution With 1.17g (5.53mmol) 1- iodohexanes, all the elements thing is stirred 5 hours in 25 DEG C.After the completion of reaction, by reaction solution Input is into 100ml water, with 300ml ethyl acetate extraction.By ethyl acetate layer anhydrous sodium sulfate drying, sulfuric acid is filtered out Sodium.Ethyl acetate is distilled off from filtrate decompression with rotary evaporator, faint yellow solid is obtained.The faint yellow solid is passed through into silicon Glue column chromatography (hexane:Ethyl acetate=90:10) purify, 545mg intermediate M (yields are obtained as white solid： 39.4%).
The structure of object passes through1H-NMR is identified.
1H-NMR(500MHz,CDCl3,TMS,δppm)：8.57 (d, 1H, J=8.0Hz), 7.85 (d, 1H, J=8.0Hz), 7.69 (d, 1H, J=8.5Hz), 7.532 (d, 1H, J=8.5Hz), 7.531 (dd, 1H, J=7.5Hz, 8.0Hz), 7.46 (dd, 1H, J=7.5Hz, 8.0Hz), 4.27 (s, 2H), 3.83 (t, 2H, J=7.5Hz), 1.76 (tt, 2H, J=7.5Hz, 7.5Hz), 1.34-1.45 (m, 6H), 0.90 (t, 3H, J=7.0Hz).
Step 4：Intermediate N synthesis
[changing 56]
545mg (1.82mmol) 2,5- dihydroxy benzenes is added into the four neck reactors for possess thermometer in nitrogen stream The 1- propyl alcohol of formaldehyde, 1.40g (1.40mmol) intermediate M and 10ml that are synthesized in above-mentioned steps 3, is made uniform molten Liquid.42.3mg (0.18mmol) (±) -10- camphorsulfonic acids are added into the solution, all the elements thing is small in 25 DEG C of stirrings 4 When.After the completion of reaction, 100ml water, the solid that leaching is separated out are added.It is dry with vacuum after the solid of leaching is cleaned with water Dry machine is dried, and 588mg intermediate N (yields are obtained as yellow solid：76.9%).
The structure of object passes through1H-NMR is identified.
1H-NMR(500MHz,DMSO-d6,TMS,δppm)：9.42 (s, 1H), 8.99 (s, 1H), 8.51 (d, 1H, J= 8.0Hz), 8.19 (s, 1H), 7.98 (d, 1H, J=8.0Hz), 7.96 (d, 1H, J=8.5Hz), 7.70 (d, 1H, J= 8.5Hz), 7.61 (dd, 1H, J=7.5Hz, 8.0Hz), 7.54 (dd, 1H, J=7.5Hz, 8.0Hz), 7.22 (d, 1H, J= 3.0Hz), 6.78 (d, 1H, J=9.0Hz), 6.71 (dd, 1H, J=3.0Hz, 9.0Hz), 4.47 (t, 2H, J=7.0Hz), 1.75 (tt, 2H, J=7.0Hz, 7.0Hz), 1.38-1.46 (m, 4H), 1.26-1.33 (m, 2H), 0.86 (t, 3H, J= 7.5Hz)。
Step 5：The synthesis of compound 5
In nitrogen stream into the four neck reactors for possess thermometer add 588mg (1.40mmol) in above-mentioned steps 4 Intermediate N, 1.47g (3.50mmol) of the middle synthesis intermediate A synthesized in embodiment 1,85.5mg (0.70mmol) The 1-METHYLPYRROLIDONE of 4- (dimethylamino) pyridines and 15ml, is made uniform solution.805mg is added into the solution 1- ethyls -3- (3- dimethylamino-propyls) carbodiimide hydrochloride (WSC) of (4.20mmol), by all the elements thing in 25 DEG C Stirring 5 hours.After the completion of reaction, reaction solution is put into 150ml water, with 300ml ethyl acetate extraction.By acetic acid Methacrylate layer anhydrous sodium sulfate drying, filters out sodium sulphate.Ethyl acetate is distilled off from filtrate decompression with rotary evaporator, obtains White solid.The white solid is passed through into silica gel column chromatography (toluene:Ethyl acetate=90:10) purify, be used as white solid Obtain the 1.12g (yield of compound 5：65.5%).
The structure of object passes through1H-NMR is identified.
1H-NMR(500MHz,CDCl3,TMS,δppm)：8.63 (d, 1H, J=8.0Hz), 7.89 (d, 1H, J=8.0Hz), 7.78 (d, 1H, J=2.5Hz), 7.76 (d, 1H, J=8.5Hz), 7.63 (d, 1H, J=8.5Hz), 7.58 (dd, 1H, J= 7.5Hz, 8.0Hz), 7.50 (dd, 1H, J=7.5Hz, 8.0Hz), 7.13 (d, 1H, J=9.0Hz), 7.10 (dd, 1H, J= 2.5Hz, 9.0Hz), 6.99 (d, 2H, J=9.0Hz), 6.98 (d, 2H, J=9.0Hz), 6.88 (d, 4H, J=9.0Hz), 6.40 (dd, 2H, J=1.5Hz, 17.0Hz), 6.13 (dd, 2H, J=10.5Hz, 17.0Hz), 5.82 (dd, 2H, J=1.5Hz, 10.5Hz), 4.42 (t, 2H, J=7.5Hz), 4.17 (t, 4H, J=6.5Hz), 3.94 (t, 4H, J=6.0Hz), 3.47 (d, 1H, J=4.5Hz), 2.57-2.71 (m, 4H), 2.30-2.35 (m, 8H), 1.76-1.82 (m, 6H), 1.66-1.74 (m, 12H), 1.32-1.54 (m, 14H), 0.92 (t, 3H, J=7.5Hz).
The synthesis of (embodiment 6) compound 6
[changing 57]
Step 1：Intermediate O synthesis
[changing 58]
3.46g (26.7mmol) 2- amino -3- chlorine is added into the four neck reactors for possess thermometer in nitrogen stream The DMF of pyrazine, 8.56g (53.4mmol) ehtyl potassium xanthate and 30ml, is made uniform solution.The solution is heated to reflux After 7 hours, reaction solution is cooled to 0 DEG C, 3.3ml (53.4mmol) iodomethane is added, all the elements thing is stirred 1 in 0 DEG C Hour.After the completion of reaction, reaction solution is put into 300ml water, with 500ml ethyl acetate extraction.By ethyl acetate Layer anhydrous sodium sulfate drying, filters out sodium sulphate.Ethyl acetate is distilled off from filtrate decompression with rotary evaporator, yellow is obtained Solid.The yellow solid is passed through into silica gel column chromatography (toluene:Ethyl acetate=90:10) purify, obtained as faint yellow solid To 4.38g intermediate O (yields：89.5%).
The structure of object passes through1H-NMR and13C-NMR is identified.
1H-NMR(500MHz,CDCl3,TMS,δppm)：8.55 (d, 1H, J=2.5Hz), 8.37 (d, 1H, J=2.5Hz), 2.88(s,3H)
13C-NMR(125MHz,CDCl3,TMS,δppm)：175.2、158.0、153.3、141.7、139.4、15.4.
Step 2：Intermediate P synthesis
[changing 59]
In nitrogen stream into the four neck reactors for possess thermometer add 1.50g (8.19mmol) in above-mentioned steps 1 Intermediate O, 4.0ml (81.9mmol) of middle synthesis hydrazine monohydrate and 10ml ethanol, are made uniform solution, will be all Content is stirred 5 hours in 25 DEG C.After the completion of reaction, reaction solution is put into 100ml water, the solid that leaching is separated out. After the solid of leaching is cleaned with water, dried with vacuum drier, 1.15g intermediate P (yields are obtained as yellow solid： 84.0%).
The structure of object passes through1H-NMR and13C-NMR is identified.
1H-NMR(400MHz,DMSO-d6,TMS,δppm)：9.99 (brs, 1H), 8.17 (d, 1H, J=2.6Hz), 7.97 (d, 1H, J=2.6Hz), 5.30 (s, 2H)
13C-NMR(100MHz,DMSO-d6,TMS,δppm)：175.5、160.4、150.8、140.7、135.3.
Step 3：The synthesis of compound 6
In nitrogen stream into the four neck reactors for possess thermometer add 390mg (2.34mmol) in above-mentioned steps 2 Intermediate P, 2.08g (2.22mmol) of the middle synthesis intermediate B synthesized in embodiment 1,3ml ethanol and 15ml THF, is made uniform solution.54.4mg (0.23mmol) (±) -10- camphorsulfonic acids are added into the solution, will be all interior It is tolerant to be stirred 5 hours in 40 DEG C.After the completion of reaction, reaction solution is put into 150ml water, with 300ml ethyl acetate Extraction.By ethyl acetate layer anhydrous sodium sulfate drying, sodium sulphate is filtered out.Vinegar is distilled off from filtrate decompression with rotary evaporator Acetoacetic ester, obtains faint yellow solid.The faint yellow solid is passed through into silica gel column chromatography (chloroform:Methanol=95:5) purify, make 1.82g (the yield of compound 6 is obtained for faint yellow solid：75.3%).
The structure of object passes through1H-NMR is identified.
1H-NMR (500MHz, CDCl3,TMS,δppm)：13.00 (brs, 1H), 8.84 (s, 1H), 8.33 (d, 1H, J= 2.5Hz), 8.22 (d, 1H, J=2.5Hz), 7.71 (d, 1H, J=2.5Hz), 7.19 (dd, 1H, J=2.5Hz, 9.0Hz), 7.14 (d, 1H, J=9.0Hz), 6.99 (d, 2H, J=9.0Hz), 6.96 (d, 2H, J=9.0Hz), 6.88 (d, 2H, J= 9.0Hz), 6.86 (d, 2H, J=9.0Hz), 6.403 (dd, 1H, J=1.5Hz, 17.5Hz), 6.398 (dd, 1H, J=1.5Hz, 17.5Hz), 6.13 (dd, 1H, J=10.5Hz, 17.5Hz), 6.12 (dd, 1H, J=10.5Hz, 17.5Hz), 5.822 (dd, 1H, J=1.5Hz, 10.5Hz), 5.817 (dd, 1H, J=1.5Hz, 10.5Hz), 4.18 (t, 2H, J=7.0Hz), 4.17 (t, 2H, J=7.0Hz), 3.95 (t, 2H, J=6.5Hz), 3.93 (t, 2H, J=6.5Hz), 2.59-2.66 (m, 3H), 2.46- 2.52(m,1H)、2.17-2.34(m,8H)、1.41-1.82(m,24H)。
The synthesis of (embodiment 7) compound 7
[changing 60]
Step 1：Intermediate Q synthesis
[changing 61]
Add into the four neck reactors for possess thermometer in nitrogen stream 4.17g (24.9mmol) in embodiment 6 The intermediate P and 30ml that are synthesized in step 2 DMF, are made uniform solution.16.2g (49.8mmol) is added into the solution Cesium carbonate and 4.4ml (29.9mmol) 1- iodohexanes, by all the elements thing in 25 DEG C stir 5 hours.After the completion of reaction, Reaction solution is put into 200ml water, with 300ml ethyl acetate extraction.By ethyl acetate layer anhydrous sodium sulfate drying, Filter out sodium sulphate.Ethyl acetate is distilled off from filtrate decompression with rotary evaporator, white solid is obtained.The white solid is led to Cross silica gel column chromatography (toluene:Ethyl acetate=60:40) purify, 1.69g intermediate Q (yields are obtained as white solid： 27.0%).
The structure of object passes through1H-NMR is identified.
1H-NMR(500MHz,DMSO-d6,TMS,δppm)：8.22 (d, 1H, J=3.0Hz), 8.02 (d, 1H, J= 3.0Hz), 5.65 (s, 2H), 3.78 (t, 2H, J=7.0Hz), 1.71 (tt, 2H, J=7.0Hz, 7.0Hz), 1.26-1.32 (m, 6H), 0.86 (t, 3H, J=7.0Hz).
Step 2：The synthesis of compound 7
In nitrogen stream into the four neck reactors for possess thermometer add 338mg (1.34mmol) in above-mentioned steps 1 Intermediate Q, 1.20g (1.28mmol) of the middle synthesis intermediate B synthesized in embodiment 1,3ml ethanol and 10ml THF, is made uniform solution.15.6mg (0.13mmol) (±) -10- camphorsulfonic acids are added into the solution, will be all interior It is tolerant to be stirred 5 hours in 40 DEG C.After the completion of reaction, reaction solution is put into 100ml water, with 300ml ethyl acetate Extraction.By ethyl acetate layer anhydrous sodium sulfate drying, sodium sulphate is filtered out.Vinegar is distilled off from filtrate decompression with rotary evaporator Acetoacetic ester, obtains white solid.The white solid is passed through into silica gel column chromatography (toluene:Ethyl acetate=90:10) purify, make 1.21g (the yield of compound 7 is obtained for white solid：79.4%).
The structure of object passes through1H-NMR is identified.
1H-NMR(500MHz,CDCl3,TMS,δppm)：8.39 (d, 1H, J=2.5Hz), 8.20 (d, 1H, J=2.5Hz), 7.84 (s, 1H), 7.75 (d, 1H, J=2.0Hz), 7.14-7.18 (m, 2H), 6.99 (d, 2H, J=9.0Hz), 6.98 (d, 2H, J=9.0Hz), 6.88 (d, 4H, J=9.0Hz), 6.40 (dd, 2H, J=1.5Hz, 17.5Hz), 6.13 (dd, 2H, J= 10.5Hz, 17.5Hz), 5.82 (dd, 2H, J=1.5Hz, 10.5Hz), 4.36 (t, 2H, J=7.5Hz), 4.18 (t, 4H, J= 6.5Hz), 3.95 (t, 4H, J=6.5Hz), 2.56-2.72 (m, 4H), 2.25-2.36 (m, 8H), 1.69-1.83 (m, 18H), 1.41-1.54 (m, 10H), 1.30-1.39 (m, 4H), 0.90 (t, 3H, J=7.0Hz).
The synthesis of (embodiment 8) compound 8
[changing 62]
Step 1：Intermediate R synthesis
[changing 63]
It is in nitrogen stream that 8.89g (56.4mmol) 4- amino -5- is chloro- in the four neck reactors for possessing thermometer 2,6- dimethyl pyrimidines and 18.1g (113mmol) ehtyl potassium xanthate are dissolved in 100ml DMF.The solution is heated back Reaction solution is cooled to 0 DEG C by stream after 8 hours, adds 7.0ml (113mmol) iodomethane, is stirred 1 hour in 0 DEG C.In reaction After end, reaction solution is put into 500ml water, with 700ml ethyl acetate extraction.By ethyl acetate layer anhydrous slufuric acid After sodium is dried, sodium sulphate is filtered out.Ethyl acetate is distilled off from filtrate decompression with rotary evaporator, yellow solid is obtained.Should Yellow solid passes through silica gel column chromatography (toluene:Ethyl acetate=80:20) purify, obtain 6.88g's as faint yellow solid Intermediate R (yields：57.7%).
The structure of object passes through1H-NMR is identified.
1H-NMR(400MHz,CDCl3,TMS,δppm)：2.83(s,3H)、2.79(s,3H)、2.67(s,3H).
Step 2：Intermediate S synthesis
[changing 64]
In the four neck reactors for possessing thermometer, in nitrogen stream by 4.54g (21.5mmol) in above-mentioned steps 1 Intermediate R, 10.0ml (215mmol) of synthesis hydrazine monohydrate are dissolved in 80ml ethanol, and the solution is stirred in 25 DEG C Mix 2 hours.After the completion of reaction, reaction solution is put into 300ml water, the solid that leaching is separated out.The solid of leaching is used After water cleaning, dried with vacuum drier, 4.12g intermediate S (yields are obtained as faint yellow solid：98.1%).
The structure of object passes through1H-NMR and13C-NMR is identified.
1H-NMR(500MHz,DMSO-d6,TMS,δppm)：10.08(s,1H)、5.36(s,2H)、2.48(s,3H)、2.45 (s,3H)
13C-NMR(125MHz,DMSO-d6,TMS,δppm)：178.2、170.9、167.8、156.3、118.0、25.3、 23.2。
Step 3：The synthesis of compound 8
In the four neck reactors for possessing thermometer, in nitrogen stream by 460mg (2.36mmol) in step 2 above The intermediate S and 2.00g (2.12mmol) of the synthesis intermediate B synthesized in embodiment 1 are dissolved in 3ml ethanol and 20ml THF in the mixed solvent.54.8mg (0.24mmol) (±) -10- camphorsulfonic acids are added into the solution, by all the elements Thing is stirred 3 hours in 40 DEG C.After the completion of reaction, reaction solution is put into 150ml water, extracted with 300ml ethyl acetate Take.After ethyl acetate layer anhydrous sodium sulfate drying, sodium sulphate is filtered out.Vinegar is distilled off from filtrate decompression with rotary evaporator Acetoacetic ester, obtains yellow solid.The yellow solid is passed through into silica gel column chromatography (chloroform:Methanol=90:10) purify, be used as Huang Color solid obtains the 1.02g (yield of compound 8：43.1%).
The structure of object passes through1H-NMR is identified.
1H-NMR(500MHz,CDCl3,TMS,δppm)：13.51 (brs, 1H), 8.85 (s, 1H), 7.72 (d, 1H, J= 2.5Hz), 7.18 (dd, 1H, J=2.5Hz, 8.8Hz), 7.13 (d, 1H, J=8.8Hz), 6.98 (d, 2H, J=9.0Hz), 6.95 (d, 2H, J=9.0Hz), 6.88 (d, 2H, J=9.0Hz), 6.87 (d, 2H, J=9.0Hz), 6.41 (dd, 1H, J= 1.5Hz, 17.5Hz), 6.40 (dd, 1H, J=1.5Hz, 17.5Hz), 6.14 (dd, 1H, J=10.5Hz, 17.5Hz), 6.11 (dd, 1H, J=10.5Hz, 17.5Hz), 5.83 (dd, 1H, J=1.5Hz, 10.5Hz), 5.82 (dd, 1H, J=1.5Hz, 10.5Hz), 4.18 (t, 2H, J=7.5Hz), 4.17 (t, 2H, J=7.0Hz), 3.95 (t, 2H, J=6.5Hz), 3.93 (t, 2H, J=6.5Hz), 2.75 (s, 3H), 2.62 (s, 3H), 2.58-2.60 (m, 2H), 2.38-2.51 (m, 2H), 2.26-2.34 (m,4H)、2.07-2.14(m,4H)、1.63-1.82(m,10H)、1.41-1.53(m,14H)。
(synthesis example 1) compound A synthesis
[changing 65]
Step 1：Intermediate α synthesis
[changing 66]
20g (144.8mmol) 2,5- dihydroxy benzenes is added into the four neck reactors for possess thermometer in nitrogen stream 4- (6- acryloyl groups-hex- 1- bases epoxide) benzoic acid (DKSH company systems), the 5.3g of formaldehyde, 105.8g (362.0mmol) 4- (dimethylamino) pyridines and 200ml 1-METHYLPYRROLIDONE of (43.4mmol), are made uniform solution.Add thereto 83.3g (434.4mmol) 1- ethyls -3- (3- dimethylamino-propyls) carbodiimide hydrochloride (WSC), by all the elements thing Stirred 12 hours in 25 DEG C.After the completion of reaction, reaction solution is put into 1.5 liters of water, extracted with 500ml ethyl acetate Take.By ethyl acetate layer anhydrous sodium sulfate drying.Filter out after sodium sulphate, vinegar is distilled off from filtrate decompression with rotary evaporator Acetoacetic ester, obtains faint yellow solid.The faint yellow solid is passed through into silica gel column chromatography (toluene:Ethyl acetate=9:1) purify, 75g intermediate α (yields are obtained as white solid：75.4%).
The structure of object passes through1H-NMR is identified.
1H-NMR(400MHz,CDCl3,TMS,δppm)：10.20(s,1H)、8.18-8.12(m,4H)、7.78(d,1H,J =2.8Hz), 7.52 (dd, 1H, J=2.8Hz, 8.7Hz), 7.38 (d, 1H, J=8.7Hz), 7.00-6.96 (m, 4H), 6.40 (dd, 2H, J=1.4Hz, 17.4Hz), 6.12 (dd, 2H, J=10.6Hz, 17.4Hz), 5.82 (dd, 2H, J=1.4Hz, 10.6Hz), 4.18 (t, 4H, J=6.4Hz), 4.08-4.04 (m, 4H), 1.88-1.81 (m, 4H), 1.76-1.69 (m, 4H), 1.58-1.42(m,8H)。
Step 2：Compound A synthesis
In nitrogen stream into the four neck reactors for possess thermometer add 10.5g (15.3mmol) intermediate α and 80ml THF, is made uniform solution.3.0g (18.3mmol) 2- hydrazinobenzothiazoles are added and dissolved thereto.To this 18mg (0.08mmol) (±) -10- camphorsulfonic acids are added in solution, all the elements thing is stirred 3 hours in 25 DEG C.In reaction After end, reaction solution is put into 800ml 10% sodium bicarbonate aqueous solution, with 100ml ethyl acetate extraction 2 times.Will Ethyl acetate layer anhydrous sodium sulfate drying, filters out sodium sulphate.Ethyl acetate is distilled off from filtrate decompression with rotary evaporator, Obtain faint yellow solid.The faint yellow solid is passed through into silica gel column chromatography (toluene:Ethyl acetate=8:2) purify, as light Yellow solid obtains 8.0g compound A (yields：62.7%).
The structure of object passes through1H-NMR, mass spectrography identification.
1H-NMR(500MHz,DMSO-d6,TMS,δppm)：12.30(br,1H)、8.19(s,1H)、8.17-8.12(m, 4H), 7.76 (d, 1H, J=3.0Hz), 7.68 (d, 1H, J=7.5Hz), 7.45-7.39 (m, 3H), 7.28 (t, 1H, J= 8.0Hz), 7.18-7.14 (m, 4H), 7.09 (t, 1H, J=8.0Hz), 6.33 (dd, 2H, J=1.5Hz, 17.5Hz), 6.18 (dd, 2H, J=10.5Hz, 17.5Hz), 5.944 (dd, 1H, J=1.5Hz, 10.5Hz), 5.941 (dd, 1H, J=1.5Hz, 10.5Hz)、4.14-4.10(m,8H)、1.80-1.75(m,4H)、1.69-1.63(m,4H)、1.53-1.38(m,8H)
LCMS (APCI) is to C46H47N3O10S calculated value：833[M+]；Measured value：833.
For the compound 1~8 obtained in embodiment 1~8, the compound A obtained in synthesis example 1 and in following institute The compound 1r (Zeon Corporation systems, K35) of the reference example 1 used in the comparative example 1 shown, use in comparative example 2 Reference example 2 compound 2r (BASF AG's system, LC242), pass through method as shown below and determine phase transition temperature.
[changing 67]
<The measure 1 of phase transition temperature>
Weighing 10mg compound 1~8, compound A, compound 1r and 2r, directly with solid state, are sandwiched in 2 respectively Implemented glass substrate (E.H.C.Co., the Ltd. system, trade name with alignment film of polyimide of milled processed：Orientation process Glass substrate is same as below.) in.The substrate is placed on hot plate, is warming up to from 40 DEG C after 200 DEG C, 40 DEG C are cooled to again. With petrographic microscope, (Nikon Corporation systems, ECLIPSE LV100POL types are same as below.) observation heating, cooling when Institutional framework change.But, for compound 4~8, the measure of phase transition temperature is carried out in the range of 40 DEG C~250 DEG C； For compound A, the measure of phase transition temperature is carried out in the range of 50 DEG C~200 DEG C.
The phase transition temperature of measure is illustrated in following table 1.
In table 1, " C " represents Crystal, and " N " represents Nematic, and " I " represents Isotropic.Herein, Crystal tables Show that test compound is in solid phase, Nematic represents that test compound is in nematic liquid crystal phase, and Isotropic represents experimentization It is (same as below that compound is in isotropism liquid phase.).
[table 1]
Table 1
(embodiment 9, comparative example 1,2)
By the compound of each 1.0g compound 1 obtained in embodiment 1, the compound 1r of reference example 1 and reference example 2 (ADEKA company systems, Adekaoptomer N-1919 are same as below by 2r, 30mg Photoepolymerizationinitiater initiater A.), 100mg surface (AGC Seimi Chemical Co., Ltd.s system, KH-40 is same as below by activating agent A.) 1% cyclopentanone solution be dissolved in In 2.3g cyclopentanone.Use the disposable filter with 0.45 μm of micropore diameter to filter the solution, respectively obtain polymerism Composition 1,1r and 2r.
(embodiment 10,11)
By each 1.0g compound 2 and compound 3 that are obtained in embodiment 2,3,30mg Photoepolymerizationinitiater initiater A, 1% cyclopentanone solution of 100mg surfactant A is dissolved in 3.0g cyclopentanone, 0.25g dimethyl sulfoxide (DMSO).Should Solution uses the disposable filter with 0.45 μm of micropore diameter to filter, and respectively obtains polymerizable composition, polymerizable composition 2 and 3.
(embodiment 12)
By the 0.5g compound 3 obtained in embodiment 3,0.5g compound A, 30mg synthesized in synthesis example 1 Photoepolymerizationinitiater initiater A, 100mg 1% cyclopentanone solution of surfactant A be dissolved in 2.3g cyclopentanone.This is molten Liquid uses the disposable filter with 0.45 μm of micropore diameter to filter, and obtains polymerizable composition, polymerizable composition 4.
(embodiment 13)
By the 0.5g compound 3 obtained in embodiment 3, the Photoepolymerizationinitiater initiater A of 0.5g compound 2r, 30mg, 1% cyclopentanone solution of 100mg surfactant A is dissolved in 2.3g cyclopentanone.The solution is used with 0.45 μm The disposable filter filtering of micropore diameter, obtains polymerizable composition, polymerizable composition 5.
(embodiment 14)
By the 1.0g compound 4 obtained in example 4,30mg Photoepolymerizationinitiater initiater A, 100mg surface-active Agent A 1% cyclopentanone solution is dissolved in 2.3g cyclopentanone.By disposable mistake of the solution with 0.45 μm of micropore diameter Filter is filtered, and obtains polymerizable composition, polymerizable composition 6.
(embodiment 15)
By the 1.0g compound 5 obtained in embodiment 5,30mg Photoepolymerizationinitiater initiater A, 100mg surface-active Agent A 1% cyclopentanone solution is dissolved in 2.9g chloroform.By disposable filtering of the solution with 0.45 μm of micropore diameter Device is filtered, and obtains polymerizable composition, polymerizable composition 7.
(embodiment 16)
By the 0.5g compound 5 obtained in embodiment 5, the Photoepolymerizationinitiater initiater A of 0.5g compound A, 30mg, 1% cyclopentanone solution of 100mg surfactant A is dissolved in 2.2g cyclopentanone, 1.7g chloroform.By the solution apparatus There is the disposable filter filtering of 0.45 μm of micropore diameter, obtain polymerizable composition, polymerizable composition 8.
(embodiment 17)
By the 1.0g compound 6 obtained in embodiment 6,30mg Photoepolymerizationinitiater initiater A, 200mg surface-active Agent A 1% cyclopentanone solution is dissolved in 5.3g chloroform.By disposable filtering of the solution with 0.45 μm of micropore diameter Device is filtered, and obtains polymerizable composition, polymerizable composition 9.
(embodiment 18)
By the 0.2g compound 6 obtained in embodiment 6, the Photoepolymerizationinitiater initiater A of 0.8g compound A, 30mg, 1% cyclopentanone solution of 100mg surfactant A is dissolved in 3.7g chloroform.The solution is used micro- with 0.45 μm The disposable filter filtering in aperture, obtains polymerizable composition, polymerizable composition 10.
(embodiment 19)
By the 0.5g compound 7 obtained in embodiment 7, the Photoepolymerizationinitiater initiater A of 0.5g compound A, 30mg, 1% cyclopentanone solution of 100mg surfactant A is dissolved in 2.2g cyclopentanone.The solution is used micro- with 0.45 μm The disposable filter filtering in aperture, obtains polymerizable composition, polymerizable composition 11.
(embodiment 20)
By the 0.2g compound 7 obtained in embodiment 7, the Photoepolymerizationinitiater initiater A of 0.8g compound A, 30mg, 1% cyclopentanone solution of 100mg surfactant A is dissolved in 2.2g cyclopentanone.The solution is used with 0.45 μm The disposable filter filtering of micropore diameter, obtains polymerizable composition, polymerizable composition 12.
(embodiment 21)
By the 0.5g compound 8 obtained in embodiment 8, the Photoepolymerizationinitiater initiater A of 0.5g compound A, 30mg, 1% cyclopentanone solution of 100mg surfactant A is dissolved in 8.0g chloroform.The solution is used micro- with 0.45 μm The disposable filter filtering in aperture, obtains polymerizable composition, polymerizable composition 13.
Obtained polymerizable composition, polymerizable composition 1~13,1r and 2r are polymerize by following method to obtain macromolecule.For The macromolecule arrived, carries out the measure of phase difference and the evaluation of wavelength dispersion respectively.
<The measure of phase difference and the evaluation I of wavelength dispersion>
(i) formation 1 of the liquid crystal layer of polymerizable composition, polymerizable composition is used
In the transparent glass substrate (E.H.C.Co., the Ltd. system, business that are provided with alignment film of polyimide of ground processing The name of an article：Orientation process glass substrate, it is same as below.) on, using #4 bars be coated with polymerizable composition, polymerizable composition 1~8,10~12,1r and 2r.After film is dried 1 minute at the temperature shown in following table 2, orientation process 1 minute, is formed at the temperatures shown in table 2 Liquid crystal layer.Then, 2000mJ/cm is irradiated at the temperatures shown in table 2 from the coating surface side of liquid crystal layer2Ultraviolet gathered Close, wavelength dispersion test sample is made.
(ii) formation 2 of the liquid crystal layer of polymerizable composition, polymerizable composition is used
In being provided with the transparent glass substrate of alignment film of polyimide for ground processing, it is coated with and is polymerize using #6 bars Property composition 9 and polymerizable composition, polymerizable composition 13.After film is dried 1 minute at the temperature shown in following table 2, shown in table 2 At a temperature of orientation process 1 minute, form liquid crystal layer.Then, irradiated at the temperatures shown in table 2 from the coating surface side of liquid crystal layer 2000mJ/cm2Ultraviolet polymerize, wavelength dispersion test sample is made.
(iii) measure of phase difference
For obtained sample, using ellipsometer (J.A.Woollam company system M2000U types) determine 400nm~ Phase difference between 800nm.
(iv) evaluation of wavelength dispersion
α, β value is calculated as below using the phase difference of measure, wavelength dispersion is thus evaluated.
[number 1]
α=(449.9nm phase difference)/(548.5nm phase difference)
[number 2]
β=(650.2nm phase difference)/(548.5nm phase difference)
In the case where showing the preferable wavelength dispersibility of broadband, showing anti-wavelength dispersibility, α is less than 1, β More than 1.In the case of with flat wavelength dispersion, α and β is the value of phase same level.With general usual dispersion In the case of, α is more than 1, β and is less than 1.
That is, preferably α and β is the flat wavelength dispersibility of the value of phase same level, and it is anti-more than 1 that particularly preferred α is less than 1, β Wavelength dispersibility.
By the film thickness (μm) of liquid crystal liquid crystal property polymeric membrane obtained from polymerization, the phase difference (Re) of 548.5nm wavelength, α, β Value collect and be illustrated in following table 2.
As shown in Table 2, the macromolecule of the embodiment 9~21 obtained using compound 1~8 involved in the present invention is optics Anisotropic body.In addition, the α of obtained optically anisotropic body, which is less than 1, β, is more than 1, the preferable of broadband is presented in display Wavelength dispersibility.
The synthesis of (embodiment 22) compound 9
[changing 68]
Step 1：Intermediate T synthesis
[changing 69]
In the three neck reactors for possessing thermometer, by 3.00g (17.69mmol) 2- chloro benzothiazoles in nitrogen stream It is dissolved in 3.26g (70.74mmol) methyl hydrazine in 10ml methanol, the solution is flowed back 1 hour.After the completion of reaction, Reaction solution is cooled to 25 DEG C, put into 300ml distilled water.The crystallization separated out is filtered, after being cleaned with distilled water, vacuum is done It is dry, 3.01g intermediate T is obtained with 95% yield as white solid.
The structure of object passes through1H-NMR is identified.
1H-NMR(500MHz,DMSO-d6,TMS,δppm)：7.66 (dd, 1H, J=1.0Hz, 8.0Hz), 7.36 (dd, 1H, J=1.0Hz, 8.0Hz), 7.20 (dt, 1H, J=1.0Hz, 7.5Hz), 6.99 (dt, 1H, J=1.0Hz, 7.5Hz), 5.40 (s, 2H)、3.31(s,3H)。
Step 2：The synthesis of compound 9
In the three neck reactors for possessing thermometer, the step 2 that will be synthesized in nitrogen stream in the compound 1 of embodiment 1 The intermediate B of middle synthesis：0.70g (0.75mmol) is dissolved in 15ml THF.0.15ml is added into the solution The intermediate T synthesized in above-mentioned steps 1 of the 1N hydrochloric acid and 0.27g (1.49mmol) of (0.15mmol), by all the elements thing Stirred 10 hours in 40 DEG C.Then, after reaction solution is concentrated with rotary evaporator, concentrate is passed through into silica gel column chromatography (chlorine It is imitative:THF=98:2) purify, thus obtain 0.70g compound 9 with 85% yield as faint yellow solid.
The structure of object passes through1H-NMR is identified.
1H-NMR(500MHz,CDCl3,TMS,δppm)：7.74 (t, 1H, J=1.5Hz), 7.66-7.71 (m, 2H), 7.64 (s, 1H), 7.35 (dt, 1H, J=1.0Hz, 7.5Hz), 7.18 (dt, 1H, J=1.0Hz, 7.5Hz), 7.11 (d, 2H, J= 1.5Hz), 6.99 (d, 2H, J=9.0Hz), 6.98 (d, 2H, J=9.0Hz), 6.88 (d, 4H, J=9.0Hz), 6.40 (dd, 2H, J=1.5Hz, 17.5Hz), 6.13 (dd, 2H, J=10.5Hz, 17.5Hz), 5.82 (dd, 2H, J=1.5Hz, 10.5Hz), 4.17 (t, 4H, J=6.5Hz), 3.94 (t, 4H, J=6.5Hz), 3.73 (s, 3H), 2.55-2.76 (m, 4H), 2.25-2.39 (m,8H)、1.65-1.84(m,16H)、1.41-1.55(m,8H)。
The synthesis of (embodiment 23) compound 10
[changing 70]
Step 1：Intermediate U synthesis
[changing 71]
In the three neck reactors for possessing thermometer, by 3.00g (18.16mol) 2- diazanyl benzo thiophenes in nitrogen stream Azoles is dissolved in 70ml DMF.11.83g (36.32mol) cesium carbonate is added into the solution, 0 DEG C is cooled to.With 10 minutes 3.12g (19.97mmol) iodoethane is added dropwise thereto, after completion of dropwise addition, all the elements thing is stirred 2 hours in 0 DEG C, entered One step is stirred 5 hours in 25 DEG C.After the completion of reaction, 600ml distilled water is added into reaction solution, with 100ml acetic acid second Ester is extracted 2 times.After organic layer anhydrous sodium sulfate drying, sodium sulphate is filtered out.After filtrate is concentrated with rotary evaporator, pass through Silica gel column chromatography (THF:Toluene=1:9) purify, thus obtain 1.48g intermediate with 42% yield as white solid U。
The structure of object passes through1H-NMR is identified.
1H-NMR(500MHz,DMSO-d6,TMS,δppm)：7.65 (dd, 1H, J=1.0Hz, 8.0Hz), 7.35 (dd, 1H, J=1.0Hz, 8.0Hz), 7.20 (dt, 1H, J=1.0Hz, 7.5Hz), 6.98 (dt, 1H, J=1.0Hz, 7.5Hz), 5.34 (s, 2H), 3.73 (q, 2H, J=7.0Hz), 1.20 (t, 3H, J=7.0Hz).
Step 2：The synthesis of compound 10
In the three neck reactors for possessing thermometer, by 0.70g (0.75mmol) change in embodiment 1 in nitrogen stream The intermediate B synthesized in the step 2 that compound 1 is synthesized is dissolved in 15ml THF.0.15ml is added into the solution The intermediate U synthesized in above-mentioned steps 1 of the 1N hydrochloric acid and 0.29g (1.49mmol) of (0.15mmol), by all the elements thing Stirred 10 hours in 40 DEG C.After the completion of reaction, reaction solution is concentrated with rotary evaporator, then, concentrate is passed through into silica gel Column chromatography (chloroform:THF=98:2) purify, thus obtain 0.67g compound with 81% yield as faint yellow solid 10。
The structure of object passes through1H-NMR is identified.
1H-NMR(500MHz,CDCl3,TMS,δppm)：7.75 (dd, 1H, J=1.5Hz, 2.0Hz), 7.66-7.71 (m, 3H), 7.35 (dt, 1H, J=1.0Hz, 7.5Hz), 7.17 (dt, 1H, J=1.0Hz, 7.5Hz), 7.10-7.12 (m, 2H), 6.99 (d, 2H, J=9.0Hz), 6.98 (d, 2H, J=9.0Hz), 6.88 (d, 4H, J=9.0Hz), 6.40 (dd, 2H, J= 1.5Hz, 17.5Hz), 6.13 (dd, 2H, J=10.5Hz, 17.5Hz), 5.82 (dd, 2H, J=1.5Hz, 10.5Hz), 4.38 (q, 2H, J=7.0Hz), 4.18 (t, 4H, J=6.5Hz), 3.95 (t, 4H, J=6.5Hz), 2.55-2.76 (m, 4H), 2.26- 2.40 (m, 8H), 1.65-1.84 (m, 16H), 1.41-1.55 (m, 8H), 1.34 (t, 3H, J=7.0Hz).
The synthesis of (embodiment 24) compound 11
[changing 72]
Step 1：Intermediate V synthesis
[changing 73]
In the three neck reactors for possessing thermometer, by 3.00g (18.16mol) 2- diazanyl benzo thiophenes in nitrogen stream Azoles is dissolved in 70ml DMF.11.83g (36.32mol) cesium carbonate is added into the solution and 0 DEG C, addition is cooled to 3.33g (27.23mmol) 2- N-Propyl Bromides are further small in 25 DEG C of stirrings 20 by all the elements thing after 0 DEG C is stirred 1 hour When.Then, 600ml distilled water is added into reaction solution, with 100ml ethyl acetate extraction 2 times.By the anhydrous sulphur of organic layer After sour sodium is dried, sodium sulphate is filtered out.After filtrate is concentrated with rotary evaporator, concentrate is passed through into silica gel column chromatography (THF: Toluene=1:9) purify, thus obtain 1.11g intermediate V with 29% yield as white solid.
The structure of object passes through1H-NMR is identified.
1H-NMR(500MHz,DMSO-d6,TMS,δppm)：7.65 (dd, 1H, J=1.0Hz, 8.0Hz), 7.35 (dd, 1H, J=1.0Hz, 8.0Hz), 7.20 (dt, 1H, J=1.0Hz, 7.5Hz), 6.98 (dt, 1H, J=1.0Hz, 7.5Hz), 5.10 (s, 2H), 4.61-4.72 (m, 1H), 1.17 (d, 6H, J=6.5Hz).
Step 2：The synthesis of compound 11
In the three neck reactors for possessing thermometer, by 1.4g (1.49mmol) change in embodiment 1 in nitrogen stream The intermediate B synthesized in the step 2 that compound 1 is synthesized is dissolved in 30ml THF.0.30ml is added into the solution The intermediate V synthesized in above-mentioned steps 1 of the 1N hydrochloric acid and 0.62g (2.98mmol) of (0.30mmol), by all the elements thing Stirred 10 hours in 40 DEG C.Then, after reaction solution is concentrated with rotary evaporator, concentrate is passed through into silica gel column chromatography (chlorine It is imitative:THF=98:2) purify, thus obtain 1.40g compound 11 with 83% yield as faint yellow solid.
The structure of object passes through1H-NMR is identified.
1H-NMR(500MHz,CDCl3,TMS,δppm)：8.08 (s, 1H), 7.74 (d, 1H, J=2.5Hz), 7.69 (dd, 1H, J=1.0Hz, 8.0Hz), 7.65 (d, 1H, J=8.0Hz), 7.33 (dt, 1H, J=1.0Hz, 7.5Hz), 7.16 (dt, 1H, J=1.0Hz, 7.5Hz), 7.08-7.13 (m, 2H), 6.99 (d, 2H, J=9.0Hz), 6.98 (d, 2H, J=9.0Hz), 6.88 (d, 4H, J=9.0Hz), 6.40 (dd, 2H, J=1.5Hz, 17.5Hz), 6.13 (dd, 2H, J=10.5Hz, 17.5Hz), 5.82 (dd, 2H, J=1.5Hz, 10.5Hz), 5.29-5.39 (m, 1H), 4.17 (t, 4H, J=6.5Hz), 3.94 (t, 4H, J= 6.5Hz), 2.54-2.74 (m, 4H), 2.25-2.39 (m, 8H), 1.65-1.84 (m, 16H), 1.62 (d, 6H, J=7.0Hz), 1.41-1.55(m,8H)。
The synthesis of (embodiment 25) compound 12
[changing 74]
Step 1：Intermediate W synthesis
[changing 75]
In the three neck reactors for possessing thermometer, by 3.00g (17.69mmol) 2- chloro benzothiazoles in nitrogen stream It is dissolved in 5.38g (70.74mmol) 2- hydrazinoethanols in 10ml methanol.The solution is heated to reflux 2 hours, then, Reaction solution is cooled to 25 DEG C, put into 300ml distilled water.The crystallization separated out is filtered, after being cleaned with distilled water, vacuum is done It is dry, 3.27g intermediate W is obtained with 88% yield as white solid.
The structure of object passes through1H-NMR is identified.
1H-NMR(500MHz,DMSO-d6,TMS,δppm)：7.66 (dd, 1H, J=1.0Hz, 8.0Hz), 7.35 (dd, 1H, J=1.0Hz, 8.0Hz), 7.20 (dt, 1H, J=1.0Hz, 7.5Hz), 6.98 (dt, 1H, J=1.0Hz, 7.5Hz), 5.37 (s, 2H), 4.86 (t, 1H, J=5.0Hz), 3.69-3.81 (m, 4H).
Step 2：The synthesis of compound 12
In the three neck reactors for possessing thermometer, the step 2 that will be synthesized in nitrogen stream in the compound 1 of embodiment 1 The intermediate B of middle synthesis：1.40g (1.50mmol) is dissolved in 30ml THF.0.30ml is added into the solution The intermediate W synthesized in above-mentioned steps 1 of the 1N hydrochloric acid and 0.62g (2.98mmol) of (0.30mmol) is small in 40 DEG C of stirrings 8 When.Then, after reaction solution is concentrated with rotary evaporator, silica gel column chromatography (chloroform is passed through:THF=98:2) purify, thus 1.32g compound 12 is obtained with 78% yield as faint yellow solid.
The structure of object passes through1H-NMR is identified.
1H-NMR(500MHz,CDCl3,TMS,δppm)：7.95(s,1H)、7.73-7.75(m,1H)、7.69(dd,1H,J =1.0Hz, 8.0Hz), 7.65 (d, 1H, J=8.0Hz), 7.35 (dt, 1H, J=1.0Hz, 7.5Hz), 7.18 (dt, 1H, J= 1.0Hz, 7.5Hz), 7.10-7.13 (m, 2H), 6.99 (d, 2H, J=9.0Hz), 6.98 (d, 2H, J=9.0Hz), 6.88 (d, 2H, J=9.0Hz), 6.88 (d, 2H, J=9.0Hz), 6.40 (dd, 2H, J=1.5Hz, 17.5Hz), 6.13 (dd, 2H, J= 10.5Hz, 17.5Hz), 5.82 (dd, 2H, J=1.5Hz, 10.5Hz), 4.45 (t, 2H, J=5.0Hz), 4.17 (t, 4H, J= 6.5Hz), 4.04 (q, 2H, J=5.0Hz), 3.95 (t, 2H, J=6.5Hz), 3.94 (t, 2H, J=6.5Hz), 2.85 (t, 1H, J=5.0Hz), 2.54-2.74 (m, 4H), 2.25-2.39 (m, 8H), 1.65-1.84 (m, 16H), 1.41-1.55 (m, 8H).
The synthesis of (embodiment 26) compound 13
[changing 76]
Step 1：The synthesis of intermediate X
[changing 77]
In the three neck reactors for possessing thermometer, by 3.00g (17.69mmol) 2- chloro benzothiazoles in nitrogen stream It is dissolved in 7.65g (70.74mmol) phenyl hydrazine in 30ml ethylene glycol.The solution is heated to 140 DEG C and stirring 5 is small When.After the completion of reaction, 300ml distilled water is added into reaction solution, with 100ml ethyl acetate extraction 2 times.By organic layer After anhydrous sodium sulfate drying, sodium sulphate is filtered out.After filtrate is concentrated with rotary evaporator, added into obtained concentrate 15ml THF is dissolved.The solution is put into 300ml distilled water, the solid that leaching is separated out.By filtrate distillation After water cleaning, vacuum drying is so as to obtain yellow solid.Yellow solid is added into flask, 50ml toluene and stirring is added After 30 minutes, filter removing the solid constituent insoluble in toluene.After filtrate is concentrated with rotary evaporator, it will concentrate Thing passes through silica gel column chromatography (THF:Toluene=2:50) purify, thus obtain 0.94g's as yellow oil with 22% yield Intermediate X.
The structure of object passes through1H-NMR is identified.
1H-NMR(500MHz,DMSO-d6,TMS,δppm)：8.01 (dd, 2H, J=1.0Hz, 9.0Hz), 7.78 (dd, 1H, J=1.0Hz, 8.0Hz), 7.51 (dd, 1H, J=1.0Hz, 8.0Hz), 7.43 (dd, 2H, J=7.5Hz, 8.5Hz), 7.28 (dt, 1H, J=1.0Hz, 7.5Hz), 7.08-7.16 (m, 2H), 6.26 (s, 2H).
Step 2：The synthesis of compound 13
In the three neck reactors for possessing thermometer, by 1.00g (1.06mmol) change in embodiment 1 in nitrogen stream The intermediate B synthesized in the step 2 that compound 1 is synthesized is dissolved in 30ml THF.0.22ml is added into the solution The intermediate X synthesized in above-mentioned steps 1 of the 1N hydrochloric acid and 0.38g (1.60mmol) of (0.22mmol), by all the elements thing Stirred 2 hours in 40 DEG C.After the completion of reaction, after reaction solution is concentrated with rotary evaporator, concentrate is passed through into silicagel column color Spectrometry (chloroform:THF=40:1) purify, thus obtain 1.14g compound 13 with 95% yield as faint yellow solid.
The structure of object passes through1H-NMR is identified.
1H-NMR(500MHz,CDCl3,TMS,δppm)：7.82 (d, 1H, J=2.5Hz), 7.73 (dd, 1H, J=1.0Hz, 8.0Hz), 7.64-7.70 (m, 2H), 7.60 (d, 2H, J=7.5Hz), 7.35-7.42 (m, 3H), 7.30 (dt, 1H, J= 1.0Hz, 7.5Hz), 7.18 (dt, 1H, J=1.0Hz, 7.5Hz), 7.03-7.12 (m, 2H), 7.00 (d, 2H, J=9.0Hz), 6.99 (d, 2H, J=9.0Hz), 6.90 (d, 2H, J=9.0Hz), 6.89 (d, 2H, J=9.0Hz), 6.41 (dd, 1H, J= 1.5Hz, 17.5Hz), 6.41 (dd, 1H, J=1.5Hz, 17.5Hz), 6.13 (dd, 1H, J=10.5Hz, 17.5Hz), 6.13 (dd, 1H, J=10.5Hz, 17.5Hz), 5.82 (dd, 1H, J=1.5Hz, 10.5Hz), 5.82 (dd, 1H, J=1.5Hz, 10.5Hz), 4.18 (t, 2H, J=6.5Hz), 4.18 (t, 2H, J=6.5Hz), 3.92-3.98 (m, 4H), 2.56-2.71 (m, 2H)、2.41-2.50(m,1H)、2.27-2.40(m,5H)、2.12-2.22(m,2H)、1.64-1.91(m,14H)、1.41- 1.56(m,10H)、1.19-1.31(m,2H)。
The synthesis of (embodiment 27) compound 14
[changing 78]
Step 1：Intermediate Y synthesis
[changing 79]
In the three neck reactors for possessing thermometer, by 2.50g (14.74mmol) 2- chlorobenzenes and thiophene in nitrogen stream Azoles, 7.01g (44.21mmol) to tolylhydrazine hydrochloride, 7.62g (58.95mmol) N, N- diisopropylethylamine is dissolved in In 40ml ethylene glycol.By the solution after 140 DEG C are stirred 5 hours, 400ml distilled water is added into reaction solution, 100ml is used Ethyl acetate extraction 2 times.After organic layer anhydrous sodium sulfate drying, sodium sulphate is filtered out.Filtrate is dense with rotary evaporator After contracting, 50ml toluene is added into concentrate and is stirred 30 minutes.The solid constituent insoluble in toluene is removed by filtration, will Filtrate is concentrated with rotary evaporator.Concentrate is passed through into silica gel column chromatography (THF:Toluene=5:95) purify, thus as light Yellow solid obtains 0.64g intermediate Y with 17% yield.
The structure of object passes through1H-NMR is identified.
1H-NMR(500MHz,DMSO-d6,TMS,δppm)：7.86 (d, 2H, J=8.5Hz), 7.76 (dd, 1H, J= 1.0Hz, 8.0Hz), 7.47 (dd, 1H, J=1.0Hz, 8.0Hz), 7.27 (dt, 1H, J=1.0Hz, 7.5Hz), 7.23 (d, 2H, J=8.5Hz), 7.09 (dt, 1H, J=1.0Hz, 7.5Hz), 6.19 (s, 2H), 2.31 (s, 3H).
Step 2：The synthesis of compound 14
In the three neck reactors for possessing thermometer, by 1.00g (1.06mmol) change in embodiment 1 in nitrogen stream The intermediate B synthesized in the step 2 that compound 1 is synthesized is dissolved in 30ml THF.0.22ml is added into the solution The intermediate Y synthesized in above-mentioned steps 1 of the 1N hydrochloric acid and 0.32g (1.28mmol) of (0.22mmol), by all the elements thing Stirred 1 hour in 40 DEG C.After the completion of reaction, after reaction solution is concentrated with rotary evaporator, concentrate is passed through into silicagel column color Spectrometry (chloroform:THF=40:1) purify, thus obtain 1.16g compound 14 with 93% yield as faint yellow solid.
The structure of object passes through1H-NMR is identified.
1H-NMR(500MHz,CDCl3,TMS,δppm)：7.82 (d, 1H, J=2.5Hz), 7.72 (dd, 1H, J=1.0Hz, 8.0Hz), 7.61 (dd, 1H, J=1.0Hz, 8.0Hz), 7.46 (d, 2H, J=8.0Hz), 7.40 (s, 1H), 7.25-7.32 (m, 3H), 7.17 (dt, 1H, J=1.0Hz, 7.5Hz), 7.04-7.12 (m, 2H), 6.96-7.01 (m, 4H), 6.86-6.92 (m, 4H), 6.41 (dd, 1H, J=1.5Hz, 17.5Hz), 6.41 (dd, 1H, J=1.5Hz, 17.5Hz), 6.13 (dd, 1H, J= 10.5Hz, 17.5Hz), 6.13 (dd, 1H, J=10.5Hz, 17.5Hz), 5.82 (dd, 1H, J=1.5Hz, 10.5Hz), 5.82 (dd, 1H, J=1.5Hz, 10.5Hz), 4.18 (t, 2H, J=6.5Hz), 4.18 (t, 2H, J=6.5Hz), 3.95 (t, 2H, J= 6.5Hz), 3.95 (t, 2H, J=6.5Hz), 2.55-2.72 (m, 2H), 2.50 (s, 3H), 2.41-2.50 (m, 1H), 2.27- 2.41(m,5H)、2.14-2.22(m,2H)、1.65-1.95(m,14H)、1.41-1.60(m,10H)、1.22-1.34(m,2H)。
The synthesis of (embodiment 28) compound 15
[changing 80]
Step 1：Intermediate Z synthesis
[changing 81]
In the three neck reactors for possessing thermometer, by 2.50g (14.74mmol) 2- chlorobenzenes and thiophene in nitrogen stream Azoles, 7.72g (44.21mmol) 4- methoxyphenyls hydrazine hydrochloride, 7.62g (58.95mmol) N, N- diisopropylethylamine It is dissolved in 40ml ethylene glycol.By the solution after 140 DEG C are stirred 5 hours, 400ml distilled water is added into reaction solution, With 100ml ethyl acetate extraction 2 times.After organic layer anhydrous sodium sulfate drying, sodium sulphate is filtered out.Filtrate is steamed with rotation Send out after device concentration, 50ml toluene is added into concentrate and is stirred 30 minutes.The solid insoluble in toluene is removed by filtration Composition.After filtrate is concentrated with rotary evaporator, pass through silica gel column chromatography (THF:Toluene=5:95) purify, thus as light Yellow solid obtains 0.84g intermediate Z with 21% yield.
The structure of object passes through1H-NMR is identified.
1H-NMR(500MHz,DMSO-d6,TMS,δppm)：7.82 (d, 2H, J=9.0Hz), 7.75 (dd, 1H, J= 1.0Hz, 8.0Hz), 7.43 (dd, 1H, J=1.0Hz, 8.0Hz), 7.25 (dt, 1H, J=1.0Hz, 7.5Hz), 7.07 (dt, 1H, J=1.0Hz, 7.5Hz), 7.01 (d, 2H, J=9.0Hz), 6.15 (s, 2H), 3.78 (s, 3H).
Step 2：The synthesis of compound 15
In the three neck reactors for possessing thermometer, by 1.00g (1.06mmol) change in embodiment 1 in nitrogen stream The intermediate B synthesized in the step 2 that compound 1 is synthesized is dissolved in 30ml THF.0.22ml is added into the solution The intermediate Z synthesized in above-mentioned steps 1 of the 1N hydrochloric acid and 0.34g (1.28mmol) of (0.22mmol), by all the elements thing Stirred 1 hour in 40 DEG C.After the completion of reaction, after reaction solution is concentrated with rotary evaporator, concentrate is passed through into silicagel column color Spectrometry (chloroform:THF=40:1) purify, thus obtain 1.18g compound 15 with 93% yield as faint yellow solid.
The structure of object passes through1H-NMR is identified.
1H-NMR(500MHz,CDCl3,TMS,δppm)：7.82 (d, 1H, J=2.5Hz), 7.72 (dd, 1H, J=1.0Hz, 8.0Hz), 7.62 (dd, 1H, J=1.0Hz, 8.0Hz), 7.39 (s, 1H), 7.26-7.33 (m, 3H), 7.13-7.19 (m, 3H), 7.04-7.12 (m, 2H), 6.96-7.02 (m, 4H), 6.86-6.92 (m, 4H), 6.41 (dd, 1H, J=1.5Hz, 17.5Hz), 6.41 (dd, 1H, J=1.5Hz, 17.5Hz), 6.13 (dd, 1H, J=10.5Hz, 17.5Hz), 6.13 (dd, 1H, J= 10.5Hz, 17.5Hz), 5.82 (dd, 1H, J=1.5Hz, 10.5Hz), 5.82 (dd, 1H, J=1.5Hz, 10.5Hz), 4.18 (t, 2H, J=6.5Hz), 4.18 (t, 2H, J=6.5Hz), 3.95 (t, 2H, J=6.5Hz), 3.95 (t, 2H, J=6.5Hz), 3.88(s,3H)、2.55-2.72(m,2H)、2.25-2.51(m,6H)、2.13-2.22(m,2H)、1.65-1.96(m,14H)、 1.41-1.59(m,10H)、1.19-1.31(m,2H)。
The synthesis of (embodiment 29) compound 16
[changing 82]
Step 1：The synthesis of intermediate A 1
[changing 83]
In the three neck reactors for possessing thermometer, by 3.30g (20.0mol) 2- hydrazinobenzothiazoles in nitrogen stream It is dissolved in 75ml ethanol.The solution is cooled to 0 DEG C, with the isothiocyanic acid benzene that 2.70g (20.0mmol) is added dropwise for 30 minutes Ester, after completion of dropwise addition, by all the elements thing after 0 DEG C is stirred 3 hours, is further stirred 15 hours in 25 DEG C.In reaction knot Shu Hou, the crystallization that leaching is separated out in reactor.After filtrate is cleaned with ethanol, vacuum drying, as white solid with 69% yield obtains 4.14g intermediate A 1.The structure of object passes through1H-NMR is identified.
1H-NMR(500MHz,DMSO-d6,TMS,δppm)：10.22 (s, 1H), 10.09 (s, 2H), 7.80 (d, 1H, J= 7.5Hz)、7.46-7.55(m,3H)、7.26-7.36(m,3H)、7.09-7.19(m,2H)。
Step 2：The synthesis of compound 16
In the three neck reactors for possessing thermometer, by 2.50g (2.66mmol) change in embodiment 1 in nitrogen stream The intermediate B synthesized in the step 2 that compound 1 is synthesized is dissolved in 150ml THF.2.65ml is added into the solution The intermediate A 1 synthesized in above-mentioned steps 1 of the 1N hydrochloric acid and 4.0g (13.3mmol) of (2.65mmol), by all the elements thing Stirred 30 hours in 60 DEG C.After the completion of reaction, after reaction solution is concentrated with rotary evaporator, concentrate is passed through into silicagel column color Spectrometry (chloroform:THF=95:5) purify, thus obtain 1.40g compound 16 with 43% yield as faint yellow solid.
The structure of object passes through1H-NMR is identified.
1H-NMR(500MHz,CDCl3,TMS,δppm)：11.86(s,1H)、8.06(s,1H)、7.62-7.85(m,2H)、 7.28-7.59 (m, 4H), 7.06-7.25 (m, 4H), 6.80-7.05 (m, 10H), 6.40 (dd, 1H, J=1.5Hz, 17.5Hz), 6.40 (dd, 1H, J=1.5Hz, 17.5Hz), 6.13 (dd, 1H, J=10.5Hz, 17.5Hz), 6.13 (dd, 1H, J= 10.5Hz, 17.5Hz), 5.82 (dd, 1H, J=1.5Hz, 10.5Hz), 5.82 (dd, 1H, J=1.5Hz, 10.5Hz), 4.18 (t, 2H, J=6.5Hz), 4.17 (t, 2H, J=6.5Hz), 3.89-3.98 (m, 4H), 2.50-2.76 (m, 2H), 2.21-2.48 (m,6H)、1.99-2.16(m,2H)、1.35-1.85(m,26H)。
The synthesis of (embodiment 30) compound 17
[changing 84]
Step 1：The synthesis of intermediate B 1
[changing 85]
In the three neck reactors for possessing thermometer, by 2.30g (2.45mmol) change in embodiment 1 in nitrogen stream The intermediate B synthesized in the step 2 that compound 1 is synthesized is dissolved in 25ml THF.0.49ml is added into the solution The 1N hydrochloric acid of (0.49mmol), the 5ml THF solutions of 0.40g (2.45mmol) 2- hydrazinobenzothiazoles were added dropwise with 15 minutes, After completion of dropwise addition, further stirred 1 hour in 25 DEG C.After the completion of reaction, reaction solution is put into 400ml methanol, The solid that leaching is separated out.The solid of leaching is dried with vacuum drier, as faint yellow solid with yield：90% obtains 2.4g Intermediate B 1.
The structure of object passes through1H-NMR is identified.
1H-NMR(500MHz,DMSO-d6,TMS,δppm)：12.63 (s, 1H), 8.10 (s, 1H), 7.80 (d, 1H, J= 5.0Hz), 7.60 (d, 1H, J=3.0Hz), 7.48 (s, 1H), 7.21-7.35 (m, 3H), 7.14 (t, 1H, J=7.5Hz), 6.98-7.05 (m, 4H), 6.91-6.97 (m, 4H), 6.32 (dd, 2H, J=1.5Hz, 17.5Hz), 6.18 (dd, 2H, J= 10.0Hz, 17.5Hz), 5.93 (dd, 2H, J=1.5Hz, 10.0Hz), 4.12 (t, 4H, J=6.5Hz), 3.95 (t, 4H, J= 6.5Hz)、2.56-2.83(m,4H)、2.11-2.30(m,8H)、1.52-1.80(m,16H)、1.33-1.49(m,8H)。
Step 2：The synthesis of compound 17
In the three neck reactors for possessing thermometer, in nitrogen stream by 2.00g (1.84mmol) in above-mentioned steps 1 4- (dimethylamino) pyridinium dissolutions of the intermediate B 1 and 0.02g (0.18mmol) of synthesis are in 100ml THF.To the solution The positive caprylyl chloride of middle addition 0.33g (2.03mmol), reactor is impregnated in water-bath and makes temperature in reaction solution be 10 DEG C.Connect , it is after completion of dropwise addition, all the elements thing is small in 25 DEG C of stirrings 2 with the triethylamine that 0.22g (2.21mmol) is added dropwise for 10 minutes When.After the completion of reaction, 600ml distilled water and 10ml saturated aqueous common salt are added into reaction solution, is extracted with 200ml chloroform Take 2 times.After organic layer anhydrous sodium sulfate drying, sodium sulphate is filtered out.After filtrate is concentrated with rotary evaporator, by concentrate Pass through silica gel column chromatography (chloroform:THF=40:2) purify, 1.72g is thus obtained with 77% yield as faint yellow solid Compound 17.
The structure of object passes through1H-NMR is identified.
1H-NMR(500MHz,CDCl3,TMS,δppm)：8.89 (s, 1H), 7.89-7.98 (m, 2H), 7.78 (d, 1H, J= 2.5Hz), 7.53 (dt, 1H, J=1.0Hz, 7.5Hz), 7.42 (dt, 1H, J=1.0Hz, 7.5Hz), 7.20 (dd, 1H, J= 2.5Hz, 9.0Hz), 7.14 (d, 1H, J=9.0Hz), 6.98 (d, 2H, J=9.0Hz), 6.96 (d, 2H, J=9.0Hz), 6.89 (d, 2H, J=9.0Hz), 6.88 (d, 2H, J=9.0Hz), 6.40 (dd, 1H, J=1.5Hz, 17.5Hz), 6.40 (dd, 1H, J =1.5Hz, 17.5Hz), 6.13 (dd, 1H, J=10.5Hz, 17.5Hz), 6.13 (dd, 1H, J=10.5Hz, 17.5Hz), 5.82 (dd, 1H, J=1.5Hz, 10.5Hz), 5.82 (dd, 1H, J=1.5Hz, 10.5Hz), 4.18 (t, 2H, J=6.5Hz), 4.17 (t, 2H, J=6.5Hz), 3.92-3.98 (m, 4H), 3.01 (t, 2H, J=7.5Hz), 2.54-2.70 (m, 2H), 2.39- 2.48 (m, 1H), 2.23-2.37 (m, 5H), 1.91-2.06 (m, 4H), 1.62-1.86 (m, 14H), 1.26-1.56 (m, 20H), 0.90 (t, 3H, J=7.0Hz).
The synthesis of (embodiment 31) compound 18
[changing 86]
Step 1：Intermediate C1 synthesis
[changing 87]
In the four neck reactors for possessing thermometer, by 2.50g (16.6mmol) cyclohexyl hydrazonium salt acid in nitrogen stream Salt is dissolved in 8ml triethylamine.5.63g (33.2mmol) 2- chloro benzothiazoles are added into the solution, by all the elements Thing is stirred 5 hours in 80 DEG C.After the completion of reaction, reaction solution is cooled to 20 DEG C, put into 150ml saturated sodium bicarbonate water In solution, with 300ml ethyl acetate extraction.After ethyl acetate layer anhydrous sodium sulfate drying, sodium sulphate is filtered out.With rotation Ethyl acetate is distilled off from filtrate decompression in evaporator, obtains yellow solid.The yellow solid is passed through into silica gel column chromatography (oneself Alkane:Ethyl acetate=75:25) purify, 1.02g intermediate C1 (yields are obtained as white solid：22.3%).
The structure of object passes through1H-NMR is identified.
1H-NMR(400MHz,CDCl3,TMS,δppm)：7.58 (d, 1H, J=7.8Hz), 7.52 (d, 1H, J=8.2Hz), 7.26 (dd, 1H, J=7.4Hz, 8.2Hz), 7.05 (dd, 1H, J=7.4Hz, 7.8Hz), 4.25-4.32 (m, 1H), 4.04 (s, 2H)、1.84-1.88(m,4H)、1.68-1.73(m,1H)、1.43-1.59(m,4H)、1.08-1.19(m,1H)。
Step 2：The synthesis of compound 18
In the three neck reactors for possessing thermometer, add in nitrogen stream 1.40g (1.49mmol) in embodiment 1 Compound 1 synthesize step 2 in synthesize intermediate B, 456mg (1.84mmol) intermediate synthesized in above-mentioned steps 1 C1,38.6mg (0.166mmol) (±) -10- camphorsulfonic acids, 16ml THF and 4ml ethanol, are made uniform solution.So Afterwards, all the elements thing is stirred 5 hours in 40 DEG C.After the completion of reaction, reaction solution is put into 100ml water, uses 200ml Ethyl acetate extraction.By obtained ethyl acetate layer anhydrous sodium sulfate drying, sodium sulphate is filtered out.With rotary evaporator from filter Liquid vacuum distillation removes ethyl acetate, obtains yellow solid.The yellow solid is passed through into silica gel column chromatography (chloroform:THF= 97:3) purify, the 1.24g (yield of compound 18 is obtained as faint yellow solid：71.4%).
The structure of object passes through1H-NMR is identified.
1H-NMR(500MHz,CDCl3,TMS,δppm)：8.15 (s, 1H), 7.72 (d, 1H, J=1.5Hz), 7.68 (dd, 1H, J=1.5Hz, 8.0Hz), 7.66 (dd, 1H, J=1.5Hz, 8.0Hz), 7.31-7.35 (m, 1H), 7.14-7.18 (m, 1H), 7.13 (d, 1H, J=9.0Hz), 7.10 (dd, 1H, J=1.5Hz, 9.0Hz), 6.96-7.00 (m, 4H), 6.86-6.90 (m, 4H), 6.40 (dd, 2H, J=1.5Hz, 17.0Hz), 6.13 (dd, 2H, J=10.0Hz, 17.0Hz), 5.82 (dd, 2H, J =1.5Hz, 10.0Hz), 4.62-4.70 (m, 1H), 4.17 (t, 4H, J=6.5Hz), 3.94 (t, 4H, J=6.5Hz), 2.55- 2.74(m,4H)、2.27-2.47(m,10H)、1.90-2.00(m,4H)、1.65-1.85(m,16H)、1.42-1.55(m, 10H)、1.24-1.33(m,2H)。
The synthesis of (embodiment 32) compound 19
[changing 88]
Step 1：Intermediate D1 synthesis
[changing 89]
In the four neck reactors for possessing thermometer, by 5.00g (30.3mmol) 2- diazanyl benzo thiophenes in nitrogen stream Azoles is dissolved in 100ml DMF.20.9g (152mmol) potassium carbonate and 5.17g (30.3mmol) is added into the solution 5- bromine valeronitriles, all the elements thing is stirred 8 hours in 60 DEG C.After the completion of reaction, reaction solution is cooled to 20 DEG C, input is extremely In 500ml water, with 500ml ethyl acetate extraction.After ethyl acetate layer anhydrous sodium sulfate drying, sodium sulphate is filtered out. Ethyl acetate is distilled off from filtrate decompression with rotary evaporator, yellow solid is obtained.The yellow solid is passed through into silicagel column color Spectrometry (n-hexane:Ethyl acetate=60:40) purify, 3.41g intermediate D1 (yields are obtained as white solid： 45.7%).
The structure of object passes through1H-NMR is identified.
1H-NMR(400MHz,CDCl3,TMS,δppm)：7.60 (d, 1H, J=7.8Hz), 7.51 (d, 1H, J=8.1Hz), 7.28 (dd, 1H, J=7.3,8.1Hz), 7.07 (dd, 1H, J=7.3Hz, 7.8Hz), 4.23 (s, 2H), 3.81 (t, 2H, J= 6.9Hz), 2.46 (t, 2H, J=7.1Hz), 1.88-1.95 (m, 2H), 1.71-1.79 (m, 2H).
Step 2：The synthesis of compound 19
In the three neck reactors for possessing thermometer, add in nitrogen stream 1.50g (1.60mmol) in embodiment 1 Compound 1 synthesize step 2 in synthesize intermediate B, 438mg (1.78mmol) intermediate synthesized in above-mentioned steps 1 D1,41.4mg (0.178mmol) (±) -10- camphorsulfonic acids, 16ml THF and 4ml ethanol, are made uniform solution.So Afterwards, all the elements thing is stirred 5 hours in 40 DEG C.After the completion of reaction, reaction solution is put into 100ml water, uses 200ml Ethyl acetate extraction.By ethyl acetate layer anhydrous sodium sulfate drying, sodium sulphate is filtered out.With rotary evaporator from filtrate decompression Ethyl acetate is distilled off, yellow solid is obtained.The yellow solid is passed through into silica gel column chromatography (toluene:Ethyl acetate=85: 15) purify, the 1.31g (yield of compound 19 is obtained as faint yellow solid：70.2%).
The structure of object passes through1H-NMR is identified.
1H-NMR(500MHz,CDCl3,TMS,δppm)：7.74 (d, 1H, J=1.5Hz), 7.64-7.72 (m, 3H), 7.35 (ddd, 1H, J=1.5Hz, 8.0Hz, 8.0Hz), 7.19 (ddd, 1H, J=1.5Hz, 8.0Hz, 8.0Hz), 7.10-7.14 (m, 2H), 6.96-7.01 (m, 4H), 6.86-6.91 (m, 4H), 6.40 (dd, 2H, J=1.5Hz, 17.0Hz), 6.12 (dd, 2H, J =10.5Hz, 17.0Hz), 5.82 (dd, 2H, J=1.5Hz, 10.5Hz), 4.22 (t, 2H, J=6.5Hz), 4.18 (t, 4H, J =6.5Hz), 3.95 (t, 4H, J=6.5Hz), 2.58-2.75 (m, 4H), 2.55 (t, 2H, J=6.5Hz), 2.26-2.40 (m, 8H), 1.96 (tt, 2H, J=6.5Hz, 6.5Hz), 1.66-1.83 (m, 18H), 1.42-1.55 (m, 8H).
The synthesis of (embodiment 33) compound 20
[changing 90]
Step 1：The synthesis of intermediate E 1
[changing 91]
In the three neck reactors for possessing thermometer, by 2.00g (12.1mmol) 2- diazanyl benzo thiophenes in nitrogen stream Azoles is dissolved in 30ml DMF.7.88g (24.2mol) cesium carbonate is added into the solution and 0 DEG C is cooled to, with 5 minutes drops Plus 3.28g (14.5mmol) iodine heptane, after completion of dropwise addition, all the elements thing is stirred 3 hours in 25 DEG C.Terminate in reaction Afterwards, 200ml water is added into reaction solution, with 100ml ethyl acetate extraction 2 times.By organic layer anhydrous sodium sulfate drying Afterwards, sodium sulphate is filtered out.After filtrate is concentrated with rotary evaporator, concentrate is passed through into silica gel column chromatography (n-hexane:Acetic acid second Ester=85:15) purify, the 1.81g (yield of intermediate E 1 is thus obtained as white solid：56.9%).
The structure of object passes through1H-NMR is identified.
1H-NMR(500MHz,CDCl3,TMS,δppm)：7.59 (dd, 1H, J=1.5Hz, 8.0Hz), 7.53 (dd, 1H, J =1.5Hz, 8.0Hz), 7.06-7.28 (m, 2H), 4.22 (s, 2H), 3.75 (t, 2H, J=7.0Hz), 1.29-1.38 (m, 10H), 0.88 (t, 3H, J=7.0Hz).
Step 2：The synthesis of compound 20
Add into the three neck reactors for possess thermometer in nitrogen stream 1.50g (1.60mmol) in embodiment 1 Compound 1 synthesize step 2 in synthesize intermediate B, 468mg (1.78mmol) intermediate synthesized in above-mentioned steps 1 E1,41.4mg (0.178mmol) (±) -10- camphorsulfonic acids, 16ml THF and 4ml ethanol, are made uniform solution.So Afterwards, all the elements thing is stirred 5 hours in 40 DEG C.After the completion of reaction, reaction solution is put into 100ml water, uses 200ml Ethyl acetate extraction.By ethyl acetate layer anhydrous sodium sulfate drying, sodium sulphate is filtered out.With rotary evaporator from filtrate decompression Ethyl acetate is distilled off, yellow solid is obtained.The yellow solid is passed through into silica gel column chromatography (toluene:Ethyl acetate=9: 1) purify, the 1.46g (yield of compound 20 is obtained as faint yellow solid：77.5%).
The structure of object passes through1H-NMR is identified.
1H-NMR(500MHz,CDCl3,TMS,δppm)：7.75 (d, 1H, J=1.5Hz), 7.66-7.70 (m, 3H), 7.34 (ddd, 1H, J=1.5Hz, 8.0Hz, 8.0Hz), 7.17 (ddd, 1H, J=1.5Hz, 8.0Hz, 8.0Hz), 7.08-7.14 (m, 2H), 6.95-7.01 (m, 4H), 6.87-6.90 (m, 4H), 6.40 (dd, 2H, J=1.5Hz, 17.5Hz), 6.12 (dd, 2H, J =10.5Hz, 17.5Hz), 5.82 (dd, 2H, J=1.5Hz, 10.5Hz), 4.30 (t, 2H, J=7.0Hz), 4.18 (t, 4H, J =7.0Hz), 3.95 (t, 4H, J=7.0Hz), 2.55-2.73 (m, 4H), 2.26-2.40 (m, 8H), 1.65-1.84 (m, 16H), 1.36-1.55 (m, 14H), 1.25-1.35 (m, 4H), 0.87 (t, 3H, J=7.0Hz).
The synthesis of (embodiment 34) compound 21
[changing 92]
Step 1：Intermediate F1 synthesis
[changing 93]
In the four neck reactors for possessing thermometer, by 3.00g (18.2mmol) 2- diazanyl benzo thiophenes in nitrogen stream Azoles is dissolved in 45ml DMF.11.9g (36.4mmol) cesium carbonate, 6.45g (21.8mmol) 1- is added into the solution Iodine dodecane, all the elements thing is stirred 20 hours in 25 DEG C.After the completion of reaction, reaction solution is put into 200ml water, With 300ml ethyl acetate extraction.After ethyl acetate layer anhydrous sodium sulfate drying, sodium sulphate is filtered out.Use rotary evaporator Ethyl acetate is distilled off from filtrate decompression, yellow solid is obtained.The yellow solid is passed through into silica gel column chromatography (toluene:Vinegar Acetoacetic ester=95:5) purify, 2.93g intermediate F1 (yields are obtained as white solid：48.3%).
The structure of object passes through1H-NMR is identified.
1H-NMR(500MHz,CDCl3,TMS,δppm)：(7.60 dd, 1H, J=1.0Hz, 8.0Hz), 7.53 (dd, 1H, J =1.0Hz, 8.0Hz), 7.27 (ddd, 1H, J=1.0Hz, 7.5Hz, 8.0Hz), 7.06 (ddd, 1H, J=1.0Hz, 7.5Hz, 8.0Hz), 4.22 (s, 2H), 3.74 (t, 2H, J=7.5Hz), 1.73 (tt, 2H, J=7.5Hz, 7.5Hz), 1.41-1.25 (m, 18H), 0.88 (t, 3H, J=7.0Hz).
Step 2：The synthesis of compound 21
Add into the three neck reactors for possess thermometer in nitrogen stream 1.50g (1.60mmol) in embodiment 1 Compound 1 synthesize step 2 in synthesize intermediate B, 591mg (1.78mmol) intermediate synthesized in above-mentioned steps 1 F1,41.4mg (0.178mmol) (±) -10- camphorsulfonic acids, 16ml THF and 4ml ethanol, are made uniform solution.So Afterwards, all the elements thing is stirred 5 hours in 40 DEG C.After the completion of reaction, reaction solution is put into 100ml water, uses 200ml Ethyl acetate extraction.By ethyl acetate layer anhydrous sodium sulfate drying, sodium sulphate is filtered out.With rotary evaporator from filtrate decompression Ethyl acetate is distilled off, yellow solid is obtained.The yellow solid is passed through into silica gel column chromatography (toluene:Ethyl acetate=9: 1) purify, the 1.44g (yield of compound 21 is obtained as faint yellow solid：71.9%).
The structure of object passes through1H-NMR is identified.
1H-NMR(500MHz,CDCl3,TMS,δppm)：7.74 (d, 1H, J=1.5Hz), 7.66-7.70 (m, 3H), 7.34 (ddd, 1H, J=1.5Hz, 7.5Hz, 7.5Hz), 7.17 (ddd, 1H, J=1.5Hz, 7.5Hz, 7.5Hz), 7.08-7.14 (m, 2H), 6.95-7.01 (m, 4H), 6.86-6.91 (m, 4H), 6.41 (dd, 2H, J=1.5Hz, 17.5Hz), 6.12 (dd, 2H, J =10.5Hz, 17.5Hz), 5.82 (dd, 2H, J=1.5Hz, 10.5Hz), 4.30 (t, 2H, J=7.0Hz), 4.18 (t, 4H, J =7.0Hz), 3.94 (t, 4H, J=7.0Hz), 2.56-2.73 (m, 4H), 2.28-2.39 (m, 8H), 1.66-1.84 (m, 18H), 1.35-1.55 (m, 10H), 1.19-1.33 (m, 16H), 0.86 (t, 3H, J=7.0Hz).
The synthesis of (embodiment 35) compound 22
[changing 94]
Step 1：Intermediate G1 synthesis
[changing 95]
In the three neck reactors for possessing thermometer, by 2.00g (12.1mmol) 2- diazanyl benzo thiophenes in nitrogen stream Azoles is dissolved in 30ml DMF.7.88g (24.2mol) cesium carbonate is added into the solution and 0 DEG C is cooled to, with 5 minutes drops Plus 1.98g (14.5mmol) butyl 2- chloroethyl ethers, after completion of dropwise addition, all the elements thing is stirred 3 hours in 25 DEG C. After reaction terminates, 200ml water is added into reaction solution, with 100ml ethyl acetate extraction 2 times.By the anhydrous sulphur of organic layer After sour sodium is dried, sodium sulphate is filtered out.After filtrate is concentrated with rotary evaporator, by concentrate by silica gel column chromatography (just oneself Alkane:Ethyl acetate=75:25) purify, 1.70g intermediate G1 (yields are thus obtained as white solid：53.0%).
The structure of object passes through1H-NMR is identified.
1H-NMR(500MHz,CDCl3,TMS,δppm)：7.61 (dd, 1H, J=1.0Hz, 8.0Hz), 7.50 (dd, 1H, J =1.0Hz, 8.0Hz), 7.27-7.29 (m, 1H), 7.04-7.08 (m, 1H), 4.70 (s, 2H), 4.01 (t, 2H, J= 5.0Hz), 3.82 (t, 2H, J=5.0Hz), 3.44 (t, 2H, J=7.0Hz), 1.52-1.57 (m, 2H), 1.31-1.39 (m, 2H), 0.90 (t, 3H, J=7.0Hz).
Step 2：The synthesis of compound 22
Add into the three neck reactors for possess thermometer in nitrogen stream 1.50g (1.60mmol) in embodiment 1 Compound 1 synthesize step 2 in synthesize intermediate B, 396mg (1.78mmol) intermediate synthesized in above-mentioned steps 1 G1,41.4mg (0.178mmol) (±) -10- camphorsulfonic acids, 16ml THF and 4ml ethanol, are made uniform solution.So Afterwards, all the elements thing is stirred 5 hours in 40 DEG C.After the completion of reaction, reaction solution is put into 100ml water, uses 200ml Ethyl acetate extraction.By obtained ethyl acetate layer anhydrous sodium sulfate drying, sodium sulphate is filtered out.With rotary evaporator from filter Liquid vacuum distillation removes ethyl acetate, obtains yellow solid.The yellow solid is passed through into silica gel column chromatography (toluene:Acetic acid second Ester=9:1) purify, the 1.31g (yield of compound 22 is obtained as faint yellow solid：69.4%).
The structure of object passes through1H-NMR is identified.
1H-NMR(500MHz,CDCl3,TMS,δppm)：8.03 (s, 1H) 7.76 (d, 1H, J=1.5Hz), 7.65-7.71 (m, 2H), 7.34 (ddd, 1H, J=1.5Hz, 8.0Hz, 8.0Hz), 7.17 (ddd, 1H, J=1.5Hz, 8.0Hz, 8.0Hz), 7.09-7.12 (m, 2H), 6.96-7.00 (m, 4H), 6.87-6.90 (m, 4H), 6.40 (dd, 2H, J=1.5Hz, 17.5Hz), 6.13 (dd, 2H, J=10.5Hz, 17.5Hz), 5.82 (dd, 2H, J=1.5Hz, 10.5Hz), 4.45 (t, 2H, J=5.5Hz), 4.18 (t, 4H, J=7.0Hz), 3.95 (t, 4H, J=7.0Hz), 3.79 (t, 2H, J=5.5Hz), 3.44 (t, 2H, J= 7.0Hz)、2.55-2.74(m,4H)、2.28-2.40(m,8H)、1.65-1.83(m,16H)、1.42-1.55(m,10H)、 1.25-1.34 (m, 2H), 0.85 (t, 3H, J=7.0Hz).
The synthesis of (embodiment 36) compound 23
[changing 96]
In the three neck reactors for possessing thermometer, by 2.00g (1.84mmol) in embodiment 30 in nitrogen stream The intermediate B 1 synthesized in the step 1 that compound 17 is synthesized is dissolved in 20ml THF, is cooled to 0 DEG C.Added into the solution 344mg (2.76mmol) 2- methoxvethoxvmethvl chlorine, further with the N, N- that 476mg (3.68mmol) is added dropwise for 5 minutes The 5ml THF solutions of diisopropylethylamine.After completion of dropwise addition, all the elements thing is stirred 20 hours in 25 DEG C.In reaction knot Shu Hou, reaction solution is put into 100ml water, with 200ml ethyl acetate extraction.By ethyl acetate layer anhydrous sodium sulfate Dry, filter out sodium sulphate.Ethyl acetate is distilled off from filtrate decompression with rotary evaporator, yellow solid is obtained.By the yellow Solid passes through silica gel column chromatography (chloroform:THF=95:5) purify, the compound 23 for obtaining 1.58g as faint yellow solid (is received Rate：73.0%).
The structure of object passes through1H-NMR is identified.
1H-NMR(500MHz,DMSO-d6,TMS,δppm)：8.31(s,1H)、7.62-7.71(m,2H)、7.32-7.42 (m,2H)、7.25-7.29(m,2H)、7.15-7.19(m,1H)、7.00-7.04(m,4H)、6.92-6.96(m,4H)、6.32 (dd, 2H, J=1.5Hz, 17.5Hz), 6.17 (dd, 2H, J=10.5Hz, 17.5Hz), 5.93 (dd, 2H, J=1.5Hz, 10.5Hz), 5.60 (s, 2H), 4.12 (t, 4H, J=6.5Hz), 3.95 (t, 4H, J=6.5Hz), 3.71 (t, 2H, J= 6.0Hz), 3.46 (t, 2H, J=6.0Hz), 3.20 (s, 3H), 2.60-2.85 (m, 4H), 2.11-2.28 (m, 8H), 1.55- 1.75(m,16H)、1.35-1.50(m,8H)。
The synthesis of (embodiment 37) compound 24
[changing 97]
Step 1：The synthesis of compound 24
In the three neck reactors for possessing thermometer, by 2.00g (1.84mmol) in embodiment 30 in nitrogen stream The intermediate B 1 synthesized in the step 1 that compound 17 is synthesized is dissolved in 20ml THF, is cooled to 0 DEG C.Added into the solution 412mg (2.76mmol) chloromethylcyclohexyl ether, further with the N that 476mg (7.36mmol) is added dropwise for 5 minutes, N- diisopropyls The 5ml THF solutions of base ethamine.After completion of dropwise addition, all the elements thing is stirred 3 hours in 25 DEG C.After the completion of reaction, will Reaction solution is put into 100ml water, with 200ml ethyl acetate extraction.By ethyl acetate layer anhydrous sodium sulfate drying, filter Sulfuric acid sodium.Ethyl acetate is distilled off from filtrate decompression with rotary evaporator, yellow solid is obtained.The yellow solid is passed through Silica gel column chromatography (toluene:Ethyl acetate=95:5) purify, the 1.54g (yield of compound 24 is obtained as faint yellow solid： 70.0%).
The structure of object passes through1H-NMR is identified.
1H-NMR(500MHz,CDCl3,TMS,δppm)：8.33 (s, 1H), 7.86 (d, 1H, J=2.0Hz), 7.42 (d, 1H, J=7.5Hz), 7.25-7.29 (m, 2H), 7.08-7.13 (m, 3H), 6.96-7.00 (m, 4H), 6.86-6.90 (m, 4H), 6.41 (dd, 2H, J=1.5Hz, 17.5Hz), 6.13 (dd, 2H, J=10.5Hz, 17.5Hz), 5.82 (dd, 2H, J=1.5Hz, 10.5Hz), 5.62 (s, 2H), 4.18 (t, 4H, J=6.5Hz), 3.95 (t, 4H, J=6.5Hz), 3.56-3.64 (m, 1H), 2.57-2.76(m,4H)、2.27-2.40(m,8H)、1.89-1.95(m,2H)、1.64-1.83(m,16H)、1.42-1.55(m, 10H)、1.18-1.39(m,6H)。
The synthesis of (embodiment 38) compound 25
[changing 98]
Step 1：Intermediate H1 synthesis
[changing 99]
7.28g (66.1mmol) quinhydrones, 2.38g is added into the three neck reactors for possess thermometer in nitrogen stream The sodium hydroxide of (59.5mmol) and 50ml distilled water.9.90g (60.1mmol) 8- was added dropwise into the solution with 30 minutes Chloro- 1- n-octyl alcohols, after completion of dropwise addition, all the elements thing is flowed back 5 hours.After the completion of reaction, reaction solution is cooled to 25 DEG C, the white solid that leaching is separated out, by re crystallization from toluene of the obtained solid by 120ml, is thus obtained as white solid 7.93g intermediate H1 (yields：56.1%).
The structure of object passes through1H-NMR is identified.
1H-NMR(500MHz,DMSO-d6,TMS,δppm)：8.86 (s, 1H), 6.72 (dd, 2H, J=2.5Hz, 8.0Hz), 6.65 (dd, 2H, J=2.5Hz, 8.0Hz), 4.33 (t, 1H, J=5.0Hz), 3.82 (t, 2H, J=6.5Hz), 3.37 (dt, 2H, J=5.0Hz, 6.5Hz), 1.65 (tt, 2H, J=6.5Hz, 6.5Hz), 1.28-1.42 (m, 10H).
Step 2：The synthesis of intermediate compound I 1
[changing 100]
In nitrogen stream into the three neck reactors for possess thermometer add 7.84g (32.9mmol) in above-mentioned steps 1 Intermediate H1,2.61g (36.2mmol) of middle synthesis acrylic acid, 40.8mg (0.329mmol) 4- metoxyphenols, 316mg (3.29mmol) methanesulfonic acid and 40ml toluene, all the elements thing is flowed back 6 hours.Reaction solution is cooled to 25 DEG C Afterwards, input is into 200ml water, with 100ml ethyl acetate extraction.By ethyl acetate layer anhydrous sodium sulfate drying, filter out Sodium sulphate.Ethyl acetate is distilled off from filtrate decompression with rotary evaporator, brown solid is obtained.The brown solid is passed through into silicon Glue column chromatography (toluene:THF=95:5) purify, the 6.95g (yield of intermediate compound I 1 is obtained as white solid：71.9%).
The structure of object passes through1H-NMR is identified.
1H-NMR(500MHz,DMSO-d6,TMS,δppm)：8.86 (s, 1H), 6.72 (dd, 2H, J=2.5Hz, 9.0Hz), 6.65 (dd, 2H, J=2.5Hz, 8.0Hz), 6.31 (dd, 1H, J=1.5Hz, 17.5Hz), 6.17 (dd, 1H, J=10.5Hz, 17.5Hz), 5.93 (dd, 1H, J=1.5Hz, 10.5Hz), 4.10 (t, 2H, J=6.5Hz), 3.83 (t, 2H, J=6.5Hz), 1.58-1.68(m,4H)、1.30-1.39(m,8H)。
Step 3：Intermediate J1 synthesis
[changing 101]
6.86g (39.8mmol) anti-form-1,4- rings are added into the three neck reactors for possess thermometer in nitrogen stream The DMF of own dioctyl phthalate, 70ml THF and 14ml.2.28g (19.9mmol) mesyl chloride is added thereto, and reactor is soaked Stain is in water-bath, and it is 20 DEG C to make temperature in reaction solution.Then, while temperature remains 20~30 DEG C in by reaction solution, with 5 2.20g (21.7mmol) triethylamine is added dropwise in minute, after completion of dropwise addition, and all the elements thing is small in 25 DEG C of further stirrings 2 When.221mg (1.81mmol) 4- (dimethylamino) pyridine, 5.30g (18.1mmol) is added into obtained reactant mixture The intermediate compound I 1 synthesized in step 2 above, reactor is impregnated in water-bath again and makes in reaction solution temperature be 15 DEG C. And then, while temperature remains 20~30 DEG C in by reaction solution, with 5 minutes be added dropwise 2.20g (21.7mmol) triethylamine, After completion of dropwise addition, all the elements thing is stirred 2 hours in 25 DEG C.After the completion of reaction, 300ml steaming is added into reaction solution The saturated aqueous common salt of distilled water and 100ml, with 100ml ethyl acetate extraction 2 times.By organic layer anhydrous sodium sulfate drying, filter Sulfuric acid sodium, after filtrate is concentrated with rotary evaporator, silica gel column chromatography (toluene is passed through by concentrate:THF=85:15) it is pure Change, 5.23g intermediate J1 (yields are thus obtained as white solid：64.6%).
The structure of object passes through1H-NMR is identified.
1H-NMR(500MHz,DMSO-d6,TMS,δppm)：12.1 (s, 1H), 6.98 (dd, 2H, J=2.5Hz, 9.0Hz), 6.92 (dd, 2H, J=2.5Hz, 8.0Hz), 6.31 (dd, 1H, J=1.5Hz, 17.5Hz), 6.17 (dd, 1H, J=10.5Hz, 17.5Hz), 5.92 (dd, 1H, J=1.5Hz, 10.5Hz), 4.10 (t, 2H, J=6.5Hz), 3.93 (t, 2H, J=6.5Hz), 2.19-2.25 (m, 1H), 2.04-2.10 (m, 2H), 1.94-1.98 (m, 2H), 1.69 (tt, 2H, J=6.5Hz, 6.5Hz), 1.57-1.64(m,2H)、1.31-1.52(m,13H)。
Step 4：Intermediate K1 synthesis
[changing 102]
In the three neck reactors for possessing thermometer, in nitrogen stream by 4.00g (8.96mmol) in above-mentioned steps 3 The intermediate J1 of synthesis is dissolved in 60ml THF.1.07g (9.32mmol) mesyl chloride is added into the solution, will be anti- Answer device to be impregnated in water-bath and make temperature in reaction solution be 20 DEG C.Used while temperature remains 20~30 DEG C in by reaction solution It is added dropwise thereto after 944mg (9.32mmol) triethylamine within 5 minutes, all the elements thing is further stirred 2 hours in 25 DEG C.Connect , addition 92.0mg (0.748mmol) 4- (dimethylamino) pyridine, the 2 of 548mg (3.97mmol) into reactant mixture, Reactor, is impregnated in water-bath and makes in reaction solution temperature be 15 DEG C by 5- 4-dihydroxy benzaldehydes again, will in reaction solution it is warm Spend with the triethylamine that 944mg (9.32mmol) is added dropwise for 5 minutes while remaining 20~30 DEG C, will be all after completion of dropwise addition Content is further stirred 2 hours in 25 DEG C.After the completion of reaction, 350ml distilled water and 50ml is added into reaction solution Saturated aqueous common salt, is extracted 2 times with 150ml chloroform.By organic layer anhydrous sodium sulfate drying, sodium sulphate is filtered out.Filtrate is used After rotary evaporator concentration, concentrate is dissolved in 15ml THF.200ml methanol is added into the solution and knot is separated out Crystalline substance, the crystallization that leaching is separated out.After obtained crystallization is cleaned with methanol, vacuum drying is obtained in 2.85g as white solid Mesosome K1 (yields：72.3%).
The structure of object passes through1H-NMR is identified.
1H-NMR(500MHz,CDCl3,TMS,δppm)：10.1 (s, 1H), 7.61 (d, 1H, J=2.5Hz), 7.37 (dd, 1H, J=2.5Hz, 8.5Hz), 7.20 (d, 1H, J=8.5Hz), 6.97 (dd, 4H, J=2.0Hz, 9.0Hz), 6.88 (dd, 4H, J=2.0Hz, 9.0Hz), 6.40 (dd, 2H, J=1.5Hz, 17.5Hz), 6.12 (dd, 2H, J=10.5Hz, 17.5Hz), 5.82 (dd, 2H, J=1.5Hz, 10.5Hz), 4.16 (t, 4H, J=6.5Hz), 3.93 (t, 4H, J=6.5Hz), 2.57-2.74 (m, 4H)、2.26-2.37(m,8H)、1.65-1.80(m,16H)、1.35-1.48(m,16H)。
Step 5：The synthesis of compound 25
In nitrogen stream into the three neck reactors for possess thermometer add 1.95g (1.96mmol) in above-mentioned steps 4 In being synthesized in the step 1 that intermediate K1,441mg (1.76mmol) of middle the synthesis compound 4 in above-described embodiment 4 are synthesized Mesosome J, 45.6mg (0.196mmol) (±) -10- camphorsulfonic acids, 24ml THF and 6ml ethanol, are made uniform molten Liquid.Then, all the elements thing is stirred 5 hours in 40 DEG C.After the completion of reaction, reaction solution is put into 100ml water, used 200ml chloroform extraction.By chloroform layer anhydrous sodium sulfate drying, sodium sulphate is filtered out.Steamed with rotary evaporator from filtrate decompression Chloroform is removed in distillation, obtains yellow solid.The yellow solid is passed through into silica gel column chromatography (toluene:Ethyl acetate=95:5) it is pure Change, the 1.56g (yield of compound 25 is obtained as faint yellow solid：64.9%).
The structure of object passes through1H-NMR is identified.
1H-NMR(500MHz,CDCl3,TMS,δppm)：7.75 (d, 1H, J=1.5Hz), 7.66-7.70 (m, 3H), 7.34 (dd, 1H, J=1.5Hz, 7.8Hz), 7.09-7.18 (m, 3H), 6.96-7.00 (m, 4H), 6.86-6.90 (m, 4H), 6.41 (dd, 2H, J=1.5Hz, 17.5Hz), 6.12 (dd, 2H, J=10.5Hz, 17.5Hz), 5.81 (dd, 2H, J=1.5Hz, 10.5Hz), 4.30 (t, 2H, J=7.5Hz), 4.16 (t, 4H, J=6.5Hz), 3.94 (t, 4H, J=6.5Hz), 2.56-2.72 (m, 4H), 2.27-2.38 (m, 8H), 1.65-1.81 (m, 18H), 1.32-1.49 (m, 22H), 0.90 (t, 3H, J=7.5Hz).
The synthesis of (embodiment 39) compound 26
[changing 103]
Step 1：Intermediate L1 synthesis
[changing 104]
In the four neck reactors for possessing thermometer, by 5.00g (30.3mmol) 2- diazanyl benzo thiophenes in nitrogen stream Azoles is dissolved in 50ml DMF.14.8g (45.5mmol) cesium carbonate, 3.1ml (36.3mmol) alkene is added into the solution Propyl bromide, all the elements thing is stirred 2 hours in 25 DEG C.After the completion of reaction, reaction solution is put into 200ml water, used 300ml ethyl acetate extraction.After ethyl acetate layer anhydrous sodium sulfate drying, sodium sulphate is filtered out.With rotary evaporator from Ethyl acetate is distilled off in filtrate decompression, obtains yellow solid.The yellow solid is passed through into silica gel column chromatography (hexane:Acetic acid Ethyl ester=70:30) purify, 1.82g intermediate L1 (yields are obtained as white solid：29.0%).
The structure of object passes through1H-NMR is identified.
1H-NMR(500MHz,CDCl3,TMS,δppm)：(7.62 dd, 1H, J=1.0Hz, 7.5Hz), 7.54 (dd, 1H, J =1.0Hz, 8.0Hz), 7.29 (ddd, 1H, J=1.0Hz, 7.0Hz, 8.0Hz), 7.08 (ddd, 1H, J=1.0Hz, 7.0Hz, 7.5Hz), 5.90 (ddt, 1H, J=6.5Hz, 10.5Hz, 17.0Hz), 5.38 (ddt, 1H, J=1.0Hz, 2.5Hz, 10.5Hz), 5.34 (ddt, 1H, J=1.5Hz, 2.5Hz, 17.0Hz), 4.42 (ddd, 2H, J=1.0Hz, 1.5Hz, 6.5Hz), 4.18(s,2H)。
Step 2：The synthesis of compound 26
In the four neck reactors for possessing thermometer, in nitrogen stream by 368mg (1.77mmol) in above-mentioned steps 1 The intermediate B synthesized in the step 2 that the intermediate L1 and 1.50g (1.60mmol) of the synthesis compound 1 in embodiment 1 are synthesized It is dissolved in 3ml ethanol and 15ml THF in the mixed solvent.Into the solution add 41.2mg (0.18mmol) (±)- 10- camphorsulfonic acids, all the elements thing is stirred 5 hours in 40 DEG C.After the completion of reaction, reaction solution is put into 150ml water In, with 300ml ethyl acetate extraction.After ethyl acetate layer anhydrous sodium sulfate drying, sodium sulphate is filtered out.Use rotary evaporation Ethyl acetate is distilled off from filtrate decompression in device, obtains yellow solid.The yellow solid is passed through into silica gel column chromatography (toluene: Ethyl acetate=90:10) purify, the 1.61g (yield of compound 26 is obtained as white solid：89.6%).
The structure of object passes through1H-NMR is identified.
1H-NMR(500MHz,CDCl3,TMS,δppm)：7.74 (d, 1H, J=2.5Hz), 7.70 (dd, 1H, J=1.0Hz, 8.0Hz), 7.64-7.69 (m, 2H), 7.35 (ddd, 1H, J=1.0Hz, 7.5Hz, 8.0Hz), 7.18 (ddd, 1H, J= 1.0Hz, 7.5Hz, 7.5Hz), 7.09-7.13 (m, 2H), 6.99 (d, 2H, J=9.0Hz), 6.98 (d, 2H, J=9.0Hz), 6.88 (d, 4H, J=9.0Hz), 6.40 (dd, 2H, J=1.5Hz, 17.5Hz), 6.13 (dd, 2H, J=10.5Hz, 17.5Hz), 5.88 (ddt, 1H, J=4.5Hz, 10.5Hz, 17.5Hz), 5.82 (dd, 2H, J=1.5Hz, 10.5Hz), 5.29 (dd, 1H, J =1.0Hz, 10.5Hz), 5.19 (dd, 1H, J=1.0Hz, 17.5Hz), 4.98-4.99 (m, 2H), 4.18 (t, 4H, J= 6.5Hz), 3.95 (t, 4H, J=6.5Hz), 2.57-2.67 (m, 4H), 2.30-2.35 (m, 8H), 1.76-1.85 (m, 4H), 1.66-1.74(m,12H)、1.42-1.54(m,8H)。
The synthesis of (embodiment 40) compound 27
[changing 105]
Step 1：Intermediate M1 synthesis
[changing 106]
In the four neck reactors for possessing thermometer, by 5.04g (30.5mmol) 2- diazanyl benzo thiophenes in nitrogen stream Azoles is dissolved in 50ml DMF.14.9g (45.8mmol) cesium carbonate, 4.94g (36.6mmol) 4- is added into the solution Bromo- 1- butylene, all the elements thing is stirred 7 hours in 25 DEG C.After the completion of reaction, reaction solution is put into 200ml water, With 300ml ethyl acetate extraction.After ethyl acetate layer anhydrous sodium sulfate drying, sodium sulphate is filtered out.Use rotary evaporator Ethyl acetate is distilled off from filtrate decompression, yellow solid is obtained.The yellow solid is passed through into silica gel column chromatography (hexane:Vinegar Acetoacetic ester=70:30) purify, 4.40g intermediate M1 (yields are obtained as white solid：49.5%).
The structure of object passes through1H-NMR is identified.
1H-NMR(500MHz,CDCl3,TMS,δppm)：7.60 (dd, 1H, J=1.0Hz, 8.0Hz), 7.54 (dd, 1H, J =1.0Hz, 8.0Hz), 7.28 (ddd, 1H, J=1.0Hz, 7.5Hz, 8.0Hz), 7.06 (ddd, 1H, J=1.0Hz, 7.5Hz, 8.0Hz), 5.89 (ddt, 1H, J=7.0Hz, 10.5Hz, 17.0Hz), 5.17 (ddt, 1H, J=1.5Hz, 3.0Hz, 17.0Hz), 5.09 (ddt, 1H, J=1.0Hz, 3.0Hz, 10.5Hz), 4.26 (s, 2H), 3.85 (t, 2H, J=7.0Hz), 2.52 (dddt, 2H, J=1.0Hz, 1.5Hz, 7.0Hz, 7.0Hz).
Step 2：The synthesis of compound 27
In the four neck reactors for possessing thermometer, in nitrogen stream by 195mg (1.77mmol) in above-mentioned steps 1 The intermediate B synthesized in the step 2 that the intermediate M1 and 1.50g (1.60mmol) of the synthesis compound 1 in embodiment 1 are synthesized It is dissolved in 3ml ethanol and 15ml THF in the mixed solvent.Into the solution add 41.2mg (0.18mmol) (±)- 10- camphorsulfonic acids, all the elements thing is stirred 8 hours in 40 DEG C.After the completion of reaction, reaction solution is put into 150ml water In, with 300ml ethyl acetate extraction.After ethyl acetate layer anhydrous sodium sulfate drying, sodium sulphate is filtered out.Use rotary evaporation Ethyl acetate is distilled off from filtrate decompression in device, obtains yellow solid.The yellow solid is passed through into silica gel column chromatography (toluene: Ethyl acetate=90:10) purify, the 1.26g (yield of compound 27 is obtained as white solid：69.3%).
The structure of object passes through1H-NMR is identified.
1H-NMR(500MHz,CDCl3,TMS,δppm)：7.76 (d, 1H, J=2.5Hz), 7.67-7.70 (m, 3H), 7.35 (ddd, 1H, J=1.5Hz, 7.5Hz, 8.0Hz), 7.18 (ddd, 1H, J=1.5Hz, 7.5Hz, 8.0Hz), 7.10-7.14 (m, 2H), 6.99 (d, 2H, J=9.5Hz), 6.98 (d, 2H, J=9.5Hz), 6.88 (d, 4H, J=9.5Hz), 6.40 (dd, 2H, J =1.5Hz, 17.5Hz), 6.13 (dd, 2H, J=10.5Hz, 17.5Hz), 5.89 (ddt, 1H, J=6.5Hz, 10.5Hz, 17.0Hz), 5.82 (dd, 2H, J=1.5Hz, 10.5Hz), 5.18 (dd, 1H, J=1.5Hz, 17.0Hz), 5.15 (dd, 1H, J =1.5Hz, 10.5Hz), 4.38 (t, 2H, J=7.0Hz), 4.18 (t, 4H, J=6.5Hz), 3.95 (t, 4H, J=6.5Hz), (2.58-2.68 m, 4H), 2.51 (dt, 2H, J=6.5Hz, 7.0Hz), 2.31-2.35 (m, 8H), 1.76-1.85 (m, 4H), 1.65-1.74(m,12H)、1.41-1.54(m,8H)。
The synthesis of (embodiment 41) compound 28
[changing 107]
Step 1：Intermediate N1 synthesis
[changing 108]
In the four neck reactors for possessing thermometer, by 1.45g (8.75mmol) 2- diazanyl benzo thiophenes in nitrogen stream Azoles is dissolved in 20ml DMF.Addition 3.63g (26.3mmol) potassium carbonate, the 1 of 2.50g (10.5mmol) into the solution, 1,1- tri- fluoro- 4- iodobutanes, all the elements thing is stirred 8 hours in 80 DEG C.After the completion of reaction, reaction solution is cooled to 20 DEG C, put into 200ml water, with 300ml ethyl acetate extraction.After ethyl acetate layer anhydrous sodium sulfate drying, filter Sulfuric acid sodium.Ethyl acetate is distilled off from filtrate decompression with rotary evaporator, yellow solid is obtained.The yellow solid is passed through Silica gel column chromatography (n-hexane:Ethyl acetate=85:15) purify, the intermediate N1 for obtaining 961mg as white solid (is received Rate：39.9%).
The structure of object passes through1H-NMR is identified.
1H-NMR(500MHz,CDCl3,TMS,δppm)：7.61 (d, 1H, J=8.0Hz), 7.54 (d, 1H, J=7.8Hz), 7.30 (dd, 1H, J=7.8Hz, 7.8Hz), 7.09 (dd, 1H, J=7.8Hz, 8.0Hz), 4.24 (s, 2H), 3.81 (t, 2H, J =7.0Hz), 2.16-2.26 (m, 2H), 1.99-2.05 (m, 2H).
Step 2：The synthesis of compound 28
The step 2 in the synthesis of compound 1 of embodiment 1 is added into the three neck reactors for possessing thermometer in nitrogen stream The intermediate B of middle synthesis：1.50g (1.60mmol), the intermediate N1 synthesized in above-mentioned steps 1：489mg(1.78mmol)、 41.4mg (0.178mmol) (±) -10- camphorsulfonic acids, 16ml THF and 4ml ethanol, is made uniform solution.Then, All the elements thing is stirred 5 hours in 40 DEG C.After the completion of reaction, reaction solution is put into 100ml water, with 200ml's Chloroform is extracted.After organic layer anhydrous sodium sulfate drying, sodium sulphate is filtered out., will be dense after filtrate is concentrated with rotary evaporator Contracting thing passes through silica gel column chromatography (chloroform:THF=9:1) purify, the compound 28 for obtaining 1.47g as faint yellow solid (is received Rate：77.2%).
The structure of object passes through1H-NMR is identified.
1H-NMR(500MHz,CDCl3,TMS,δppm)：7.75(s,1H)、7.65-7.71(m,3H)、7.34(ddd,1H,J =1.0Hz, 7.5Hz, 7.5Hz), 7.17 (ddd, 1H, J=1.0Hz, 7.5Hz, 7.5Hz), 7.08-7.14 (m, 2H), 6.96- 7.01 (m, 4H), 6.86-6.91 (m, 4H), 6.40 (dd, 2H, J=1.5Hz, 17.5Hz), 6.13 (dd, 2H, J=10.5Hz, 17.5Hz), 5.82 (dd, 2H, J=1.5Hz, 10.5Hz), 4.42 (t, 2H, J=7.5Hz), 4.18 (t, 4H, J=6.5Hz), 3.95 (t, 4H, J=6.5Hz), 2.55-2.73 (m, 4H), 2.25-2.38 (m, 10H), 2.04 (tt, 2H, J=7.5Hz, 7.5Hz)、1.64-1.84(m,16H)、1.42-1.55(m,8H)。
The synthesis of (embodiment 42) compound 29
[changing 109]
Step 1：Intermediate O1 synthesis
[changing 110]
In the three neck reactors for possessing thermometer, by 2.00g (12.1mmol) 2- diazanyl benzo thiophenes in nitrogen stream Azoles is dissolved in 30ml DMF.7.88g (24.2mol) cesium carbonate is added into the solution and 0 DEG C is cooled to, with 5 minutes drops Plus 2.39g (14.5mmol) 2- bromohexanes, after completion of dropwise addition, further stirred 3 hours in 25 DEG C.After the completion of reaction, 200ml water is added into reaction solution, with 100ml ethyl acetate extraction 2 times.After organic layer anhydrous sodium sulfate drying, Filter out sodium sulphate.After filtrate is concentrated with rotary evaporator, concentrate is passed through into silica gel column chromatography (n-hexane:Ethyl acetate =93:7) purify, 1.61g intermediate O1 (yields are thus obtained as white solid：53.4%).
The structure of object passes through1H-NMR is identified.
1H-NMR(400MHz,CDCl3,TMS,δppm)：7.59 (dd, 1H, J=1.0Hz, 8.0Hz), 7.52 (dd, 1H, J =1.0Hz, 8.0Hz), 7.24-7.30 (m, 1H), 7.05 (ddd, 1H, J=1.0Hz, 8.0Hz, 8.0Hz), 3.97 (s, 2H), 1.47-1.74 (m, 3H), 1.20-1.41 (m, 7H), 0.89 (t, 3H, J=5.5Hz).
Step 2：The synthesis of compound 29
Add into the three neck reactors for possess thermometer in nitrogen stream 1.50g (1.60mmol) in embodiment 1 Compound 1 synthesize step 2 in synthesize intermediate B, 444mg (1.78mmol) intermediate synthesized in above-mentioned steps 1 O1,41.4mg (0.178mmol) (±) -10- camphorsulfonic acids, 16ml THF and 4ml ethanol, are made uniform solution.So Afterwards, all the elements thing is stirred 5 hours in 40 DEG C.After the completion of reaction, reaction solution is put into 100ml water, uses 200ml Chloroform extraction.After organic layer anhydrous sodium sulfate drying, sodium sulphate is filtered out., will after filtrate is concentrated with rotary evaporator Concentrate passes through silica gel column chromatography (toluene:Ethyl acetate=92:8) purify, 1.35g chemical combination is obtained as faint yellow solid (the yield of thing 29：72.4%).
The structure of object passes through1H-NMR is identified.
1H-NMR(500MHz,CDCl3,TMS,δppm)：8.04 (s, 1H), 7.73 (d, 1H, J=1.5Hz), 7.69 (dd, 1H, J=1.5Hz, 7.8Hz), 7.65 (dd, 1H, J=1.5Hz, 7.8Hz), 7.33 (ddd, 1H, J=1.5Hz, 7.8Hz, 7.8Hz), 7.07-7.19 (m, 3H), 6.95-7.01 (m, 4H), 6.85-6.91 (m, 4H), 6.40 (dd, 2H, J=1.5Hz, 17.5Hz), 6.13 (dd, 2H, J=10.5Hz, 17.5Hz), 5.82 (dd, 2H, J=1.5Hz, 10.5Hz), 4.18 (t, 4H, J =6.5Hz), 3.95 (t, 4H, J=6.5Hz), 2.54-2.73 (m, 4H), 2.25-2.40 (m, 8H), 1.65-1.83 (m, 16H), 1.60-1.62 (m, 2H), 1.57 (d, 3H, J=7.5Hz), 1.24-1.55 (m, 13H), 0.87 (t, 3H, J= 7.5Hz)。
The synthesis of (embodiment 43) compound 30
[changing 111]
Step 1：Intermediate P1 synthesis
[changing 112]
In the three neck reactors for possessing thermometer, by 2.00g (12.1mmol) 2- diazanyl benzo thiophenes in nitrogen stream Azoles is dissolved in 30ml DMF.7.88g (24.2mol) cesium carbonate is added into the solution and 0 DEG C is cooled to, with 5 minutes drops Plus 2.60g (14.5mmol) 3- heptyl bromides, after completion of dropwise addition, further stirred 3 hours in 25 DEG C.After the completion of reaction, 200ml water is added into reaction solution, with 100ml ethyl acetate extraction 2 times.After organic layer anhydrous sodium sulfate drying, Filter out sodium sulphate.After filtrate is concentrated with rotary evaporator, concentrate is passed through into silica gel column chromatography (n-hexane:Ethyl acetate =9:1) purify, 1.80g intermediate P1 (yields are thus obtained as white solid：56.4%).
The structure of object passes through1H-NMR is identified.
1H-NMR(500MHz,CDCl3,TMS,δppm)：7.58 (dd, 1H, J=1.0Hz, 7.5Hz), 7.51 (dd, 1H, J =1.0Hz, 7.5Hz), 7.27 (ddd, 1H, J=1.0Hz, 7.5Hz, 7.5Hz), 7.04 (ddd, 1H, J=1.0Hz, 7.5Hz, 7.5Hz), 3.94 (s, 2H), 1.48-1.72 (m, 5H), 1.18-1.41 (m, 4H), 0.91 (t, 3H, J=7.5Hz), 0.86 (t, 3H, J=7.5Hz).
Step 2：The synthesis of compound 30
Add into the three neck reactors for possess thermometer in nitrogen stream 1.50g (1.60mmol) in embodiment 1 Compound 1 synthesize step 2 in synthesize intermediate B, 468mg (1.78mmol) intermediate synthesized in above-mentioned steps 1 P1,41.4mg (0.178mmol) (±) -10- camphorsulfonic acids, 16ml THF and 4ml ethanol, are made uniform solution.So Afterwards, all the elements thing is stirred 5 hours in 40 DEG C.After the completion of reaction, reaction solution is put into 100ml water, uses 200ml Chloroform extraction.After organic layer anhydrous sodium sulfate drying, sodium sulphate is filtered out., will after filtrate is concentrated with rotary evaporator Concentrate passes through silica gel column chromatography (toluene:Ethyl acetate=9:1) purify, 1.44g chemical combination is obtained as faint yellow solid (the yield of thing 30：76.3%).
The structure of object passes through1H-NMR is identified.
1H-NMR(500MHz,CDCl3,TMS,δppm)：8.03 (s, 1H), 7.74 (d, 1H, J=3.0Hz), 7.69 (dd, 1H, J=1.0Hz, 8.0Hz), 7.64 (dd, 1H, J=1.0Hz, 8.0Hz), 7.33 (ddd, 1H, J=1.0Hz, 8.0Hz, 8.0Hz), 7.16 (ddd, 1H, J=1.0Hz, 8.0Hz, 8.0Hz), 7.07-7.14 (m, 2H), 6.96-7.01 (m, 4H), 6.86-6.91 (m, 4H), 6.40 (dd, 2H, J=1.5Hz, 17.5Hz), 6.12 (dd, 2H, J=10.5Hz, 17.5Hz), 5.82 (dd, 2H, J=1.5Hz, 10.5Hz), 4.18 (t, 4H, J=6.5Hz), 3.95 (t, 4H, J=6.5Hz), 2.55-2.72 (m, 4H), 2.26-2.40 (m, 8H), 1.65-1.91 (m, 19H), 1.23-1.55 (m, 14H), 0.94 (t, 3H, J=7.5Hz), 0.86 (t, 3H, J=7.5Hz).
The synthesis of (embodiment 44) compound 31
[changing 113]
Step 1：Intermediate Q1 synthesis
[changing 114]
14.4g (54.4mmol) the bromo- 1- 12 of 12- are added into the three neck reactors for possess thermometer in nitrogen stream Alcohol, 12.0g (59.8mmol) 4- (benzyloxy) phenol, 9.02g (65.2mmol) potassium carbonate, 1.42g (5.44mmol) The acetone of 18- crown- 6- ethers and 150ml, all the elements thing is flowed back 10 hours.After the completion of reaction, reaction solution is cooled to 25 DEG C, 300ml distilled water is added, with 200ml ethyl acetate extraction 2 times.After organic layer anhydrous sodium sulfate drying, filter out Sodium sulphate.Filtrate is concentrated with rotary evaporator, 12.2g intermediate Q1 (yields are thus obtained as white solid： 51.1%).
The structure of object passes through1H-NMR is identified.
1H-NMR(500MHz,DMSO-d6,TMS,δppm)：7.36-7.45(m,4H)、7.29-7.34(m,1H)、6.89- 6.94 (m, 2H), 6.81-6.86 (m, 2H), 5.02 (s, 2H), 4.32 (t, 1H, J=5.0Hz), 3.87 (t, 2H, J= 7.5Hz), 3.36 (t, 2H, J=7.5Hz), 1.66 (tt, 2H, J=7.5Hz, 7.5Hz), 1.20-1.43 (m, 18H).
Step 2：Intermediate R1 synthesis
[changing 115]
12.2g (27.8mmol) centre synthesized in above-mentioned steps is added into the three neck reactors for possess thermometer The methanol of body Q1,2.22g 5% palladium-activated carbon, 50ml THF and 200ml.Hydrogen balloon is installed on reactor, in nitrogen atmosphere It is lower to stir all the elements thing 21 hours in 25 DEG C.After the completion of reaction, 100ml chloroform, filter are added into reactant mixture Palladium removing-activated carbon.Organic layer rotary evaporator is concentrated and obtained 8.70g brown powder.The brown powder is dissolved in In 100ml toluene, add 2.34g (32.6mmol) acrylic acid, 36.8mg (0.296mmol) 4- metoxyphenols and 284mg (2.96mmol) methanesulfonic acid, all the elements thing is flowed back 10 hours.After the completion of reaction, reaction solution is cooled to 25 DEG C, put into 300ml water, with 200ml ethyl acetate extraction 2 times.After organic layer anhydrous sodium sulfate drying, filter out Sodium sulphate.After filtrate is concentrated with rotary evaporator, concentrate is passed through into silica gel column chromatography (toluene:Ethyl acetate=96:4) Purifying, thus obtains 5.94g intermediate R1 (yields as white solid：57.6%).
The structure of object passes through1H-NMR is identified.
1H-NMR(500MHz,DMSO-d6,TMS,δppm)：8.87(s,1H)、6.69-6.74(m,2H)、6.62-6.67 (m, 2H), 6.31 (dd, 1H, J=1.5Hz, 17.5Hz), 6.16 (dd, 1H, J=10.5Hz, 17.5Hz), 5.93 (dd, 1H, J =1.5Hz, 10.5Hz), 4.09 (t, 2H, J=6.5Hz), 3.82 (t, 2H, J=6.5Hz), 1.55-1.68 (m, 4H), 1.21- 1.42(m,16H)。
Step 3：Intermediate S1 synthesis
[changing 116]
6.20g (36.0mmol) anti-form-1,4- rings are added into the three neck reactors for possess thermometer in nitrogen stream The DMF of own dioctyl phthalate, 40ml THF and 8ml.2.06g (18.0mmol) mesyl chloride is added thereto, and reactor is impregnated It is 20 DEG C to make temperature in reaction solution in water-bath.Then, with 5 points while temperature remains 20~30 DEG C in by reaction solution 1.99g (19.6mmol) triethylamine is added dropwise in clock, after completion of dropwise addition, and all the elements thing is stirred 2 hours in 25 DEG C.And then, Add in 200mg (1.64mmol) 4- (dimethylamino) pyridine, the synthesizing in step 2 above of 5.70g (16.4mmol) Reactor, is impregnated in water-bath and makes temperature in reaction solution be 15 DEG C, temperature is remained in by reaction solution by mesosome R1 again With the triethylamine that 1.99g (19.6mmol) is added dropwise for 5 minutes while 20~30 DEG C, after completion of dropwise addition, further stirred in 25 DEG C Mix 2 hours.After the completion of reaction, 250ml distilled water and 100ml saturated aqueous common salt are added into reaction solution, with 200ml's Ethyl acetate extraction 2 times.After organic layer anhydrous sodium sulfate drying, sodium sulphate is filtered out.Filtrate is concentrated with rotary evaporator Afterwards, concentrate is passed through into silica gel column chromatography (toluene:THF=95:5) purify, thus obtained as white solid in 3.90g Mesosome S1 (yields：47.4%).
The structure of object passes through1H-NMR is identified.
1H-NMR(500MHz,DMSO-d6,TMS,δppm)：12.1(s,1H)、6.96-7.01(m,2H)、6.89-6.94 (m, 2H), 6.31 (dd, 1H, J=1.5Hz, 17.5Hz), 6.16 (dd, 1H, J=10.0Hz, 17.5Hz), 5.93 (dd, 1H, J =1.5Hz, 10.0Hz), 4.09 (t, 2H, J=7.0Hz), 3.93 (t, 2H, J=7.0Hz), 2.18-2.26 (m, 1H), 2.04- 2.10 (m, 2H), 1.93-2.00 (m, 2H), 1.69 (tt, 2H, J=7.0Hz, 7.0Hz), 1.59 (tt, 2H, J=7.0Hz, 7.0Hz)、1.20-1.52(m,21H)。
Step 4：Intermediate T1 synthesis
[changing 117]
In the three neck reactors for possessing thermometer, in nitrogen stream by 2.80g (5.58mmol) in above-mentioned steps 3 The intermediate S1 of synthesis is dissolved in 40ml THF.664mg (5.80mmol) mesyl chloride is added thereto, by reactor It is impregnated in water-bath and makes temperature in reaction solution be 20 DEG C.And then, while temperature remains 20~30 DEG C in by reaction solution With the triethylamine that 586mg (5.80mmol) is added dropwise for 5 minutes.After completion of dropwise addition, further stirred 2 hours in 25 DEG C.To obtaining Reactant mixture in add 56.6mg (0.464mmol) 4- (dimethylamino) pyridine, 320mg (2.32mmol) 2,5- bis- Reactor, is impregnated in water-bath by hydroxy benzaldehyde again, and it is 15 DEG C to make temperature in reaction solution, and temperature is kept in by reaction solution For 20~30 DEG C while, with 5 minutes be added dropwise 586mg (5.80mmol) triethylamine, after completion of dropwise addition, in 25 DEG C further Stirring 2 hours.After the completion of reaction, 300ml distilled water and 50ml saturated aqueous common salt are added into reaction solution, 150ml is used Chloroform extract 2 times.After organic layer anhydrous sodium sulfate drying, sodium sulphate is filtered out.After filtrate is concentrated with rotary evaporator, By obtained solid dissolving in 20ml THF.200ml methanol is added into the solution and crystallization is separated out.What leaching was separated out Crystallization, after obtained crystallization is cleaned with methanol, vacuum drying obtains 1.84g intermediate T1 (yields as white solid： 71.6%).
The structure of object passes through1H-NMR is identified.
1H-NMR(500MHz,CDCl3,TMS,δppm)：10.1 (s, 1H), 7.61 (d, 1H, J=2.8Hz), 7.37 (dd, 1H, J=2.8Hz, 9.0Hz), 7.20 (d, 1H, J=9.0Hz), 6.94-7.01 (m, 4H), 6.85-6.91 (m, 4H), 6.40 (dd, 2H, J=1.5Hz, 17.5Hz), 6.12 (dd, 2H, J=10.5Hz, 17.5Hz), 5.81 (dd, 2H, J=1.5Hz, 10.5Hz), 4.15 (t, 4H, J=6.5Hz), 3.93 (t, 4H, J=6.5Hz), 2.54-2.75 (m, 4H), 2.24-2.39 (m, 8H)、1.62-1.81(m,14H)、1.24-1.48(m,34H)。
Step 5：The synthesis of compound 31
In nitrogen stream into the three neck reactors for possess thermometer add 1.50g (1.36mmol) in above-mentioned steps 4 In being synthesized in the step 1 that intermediate T1,375mg (1.51mmol) of middle the synthesis compound 4 in above-described embodiment 4 are synthesized Mesosome J, 35.1mg (0.151mmol) (±) -10- camphorsulfonic acids, 24ml THF and 6ml ethanol, are made uniform molten Liquid.Then, all the elements thing is stirred 5 hours in 40 DEG C.After the completion of reaction, reaction solution is put into 150ml water, used 200ml chloroform extraction.After organic layer anhydrous sodium sulfate drying, sodium sulphate is filtered out.Filtrate is concentrated with rotary evaporator Afterwards, silica gel column chromatography (chloroform is passed through:THF=97:3) purify, the compound 31 for obtaining 1.54g as faint yellow solid (is received Rate：84.6%).
The structure of object passes through1H-NMR is identified.
1H-NMR(500MHz,CDCl3,TMS,δppm)：7.75 (d, 1H, J=2.0Hz), 7.65-7.71 (m, 3H), 7.34 (ddd, 1H, J=1.0Hz, 8.0Hz, 8.0Hz), 7.17 (ddd, 1H, J=1.0Hz, 8.0Hz, 8.0Hz), 7.08-7.14 (m, 2H), 6.95-7.01 (m, 4H), 6.86-6.91 (m, 4H), 6.40 (dd, 2H, J=1.5Hz, 17.5Hz), 6.12 (dd, 2H, J =10.5Hz, 17.5Hz), 5.81 (dd, 2H, J=1.5Hz, 10.5Hz), 4.30 (t, 2H, J=7.0Hz), 4.15 (t, 4H, J =7.0Hz), 3.94 (t, 4H, J=7.0Hz), 2.54-2.73 (m, 4H), 2.25-2.39 (m, 8H), 1.63-1.81 (m, 16H), 1.23-1.44 (m, 40H), 0.90 (t, 3H, J=7.0Hz).
The synthesis of (embodiment 45) compound 32
[changing 118]
Step 1：Intermediate U1 synthesis
[changing 119]
15.00g (87.12mmol) cis -1,4- is added into the three neck reactors for possess thermometer in nitrogen stream The THF of cyclohexyl dicarboxylic acid and 150ml.5.49g (47.92mmol) mesyl chloride is added thereto, and reactor is impregnated in water It is 15 DEG C to make temperature in reaction solution in bath.And then, with the triethylamine that 5.07g (50.09mmol) is added dropwise for 10 minutes, knot is being added dropwise Shu Hou, is further stirred 2 hours in 25 DEG C.0.53g (4.36mmol) 4- (diformazan ammonia is added into obtained reactant mixture Base) pyridine, 11.51g (43.56mmol) 4- (6- acryloxies-hex- 1- bases epoxide) phenol, reactor is impregnated again It is 15 DEG C to make temperature in reaction solution in water-bath, with the triethylamine that 5.29g (52.27mmol) is added dropwise for 10 minutes.Knot is being added dropwise Shu Hou, all the elements thing is further stirred 2 hours in 25 DEG C.After the completion of reaction, 1000ml steaming is added into reaction solution The saturated aqueous common salt of distilled water and 100ml, with 400ml ethyl acetate extraction 2 times.After organic layer anhydrous sodium sulfate drying, Filter out sodium sulphate.After filtrate is concentrated with rotary evaporator, concentrate is passed through into silica gel column chromatography (THF:Chloroform=5:95) Purifying, thus obtains 9.66g intermediate U1 as white solid with 53% yield.
The structure of object passes through1H-NMR is identified.
1H-NMR(500MHz,DMSO-d6,TMS,δppm)：12.16 (s, 1H), 6.99 (d, 2H, J=9.0Hz), 6.92 (d, 2H, J=9.0Hz), 6.32 (dd, 1H, J=1.5Hz, 17.5Hz), 6.17 (dd, 1H, J=10.0Hz, 17.5Hz), 5.93 (dd, 1H, J=1.5Hz, 10.0Hz), 4.11 (t, 2H, J=6.5Hz), 3.94 (t, 2H, J=6.5Hz), 2.71-2.79 (m, 1H)、2.41-2.48(m,1H)、1.57-1.91(m,12H)、1.34-1.50(m,4H)。
Step 2：Intermediate V1 synthesis
[changing 120]
In possessing three neck reactors of thermometer, in nitrogen stream by 2.50g (5.97mmol) in above-mentioned steps 1 The intermediate U1 of synthesis is dissolved in 30ml THF.0.70g (6.10mmol) mesyl chloride is added thereto, by reactor It is impregnated in water-bath and makes temperature in reaction solution be 15 DEG C.And then, with 5 minutes be added dropwise 0.63g (6.22mmol) triethylamine, After completion of dropwise addition, further stirred 2 hours in 25 DEG C.0.06g (0.50mmol) 4- is added into obtained reactant mixture Reactor, is impregnated in water-bath and makes by 2, the 5- 4-dihydroxy benzaldehydes of (dimethylamino) pyridine, 0.34g (2.49mmol) again Temperature is 15 DEG C in reaction solution, with the triethylamine that 0.60g (5.97mmol) is added dropwise for 5 minutes.After completion of dropwise addition, by all the elements Thing is further stirred 2 hours in 25 DEG C.After the completion of reaction, 200ml distilled water and 20ml saturation are added into reaction solution Saline solution, is extracted 2 times with 100ml chloroform.After organic layer anhydrous sodium sulfate drying, sodium sulphate is filtered out.By filtrate rotation Turn after evaporator concentration, 100ml methanol, the solid of leaching insoluble component are added into concentrate.By obtained solid first After alcohol cleaning, vacuum drying obtains 1.32g intermediate V1 as white solid with 56% yield.
The structure of object passes through1H-NMR is identified.
1H-NMR(500MHz,DMSO-d6,TMS,δppm)：10.02 (s, 1H), 7.67 (d, 1H, J=3.0Hz), 7.55 (dd, 1H, J=3.0Hz, 8.5Hz), 7.39 (d, 1H, J=8.5Hz), 7.01 (d, 4H, J=9.0Hz), 6.93 (d, 4H, J= 9.0Hz), 6.31 (dd, 2H, J=1.5Hz, 17.5Hz), 6.17 (dd, 2H, J=10.0Hz, 17.5Hz), 5.93 (dd, 2H, J =1.5Hz, 10.0Hz), 4.11 (t, 4H, J=6.5Hz), 3.94 (t, 4H, J=6.5Hz), 2.78-3.02 (m, 4H), 1.79- 2.05(m,16H)、1.55-1.76(m,8H)、1.33-1.49(m,8H)。
Step 3：The synthesis of compound 32
In the three neck reactors for possessing thermometer, in nitrogen stream by 1.20g (1.28mmol) in step 2 above The intermediate V1 of synthesis is dissolved in 30ml THF.0.26ml (0.26mmol) 1N hydrochloric acid and 0.48g is added into the solution The intermediate J synthesized in the step 1 that the compound 4 in above-described embodiment 4 of (1.92mmol) is synthesized, by all the elements thing in 40 DEG C stirring 7 hours.After the completion of reaction, reaction solution is concentrated with rotary evaporator, concentrate is passed through into silica gel column chromatography (chlorine It is imitative:THF=98:2) purify, thus obtain 1.23g compound 32 with 82% yield as faint yellow solid.
The structure of object passes through1H-NMR is identified.
1H-NMR(500MHz,CDCl3,TMS,δppm)：7.74 (d, 1H, J=2.5Hz), 7.68 (s, 1H), 7.64 (d, 1H, J=8.0Hz), 7.58 (dt, 1H, J=1.0Hz, 7.5Hz), 7.31 (dt, 1H, J=1.0Hz, 7.5Hz), 7.05-7.14 (m, 3H), 6.98 (d, 2H, J=9.0Hz), 6.96 (d, 2H, J=9.0Hz), 6.86 (d, 2H, J=9.0Hz), 6.84 (d, 2H, J=9.0Hz), 6.39 (dd, 1H, J=1.5Hz, 17.5Hz), 6.39 (dd, 1H, J=1.5Hz, 17.5Hz), 6.12 (dd, 1H, J=10.5Hz, 17.5Hz), 6.12 (dd, 1H, J=10.5Hz, 17.5Hz), 5.81 (dd, 1H, J=1.5Hz, 10.5Hz), 5.81 (dd, 1H, J=1.5Hz, 10.5Hz), 4.28 (t, 2H, J=7.5Hz), 4.17 (t, 2H, J=6.5Hz), 4.16 (t, 2H, J=6.5Hz), 3.87-3.96 (m, 4H), 2.75-2.90 (m, 4H), 2.08-2.26 (m, 8H), 1.85-2.03 (m, 8H), 1.65-1.82 (m, 10H), 1.24-1.54 (m, 14H), 0.87 (t, 3H, J=7.0Hz).
(embodiment 46) compound 33
[changing 121]
Step 1：Intermediate W1 synthesis
[changing 122]
In possessing three neck reactors of thermometer, by 1.50g (3.58mmol) change in embodiment 1 in nitrogen stream The intermediate A synthesized in the step 1 that compound 1 is synthesized is dissolved in 30ml THF.Then, 0.43g (3.76mmol) first is added Sulfonic acid chloride, reactor is impregnated in water-bath and makes temperature in reaction solution be 15 DEG C.0.40g was added dropwise thereto with 5 minutes The triethylamine of (3.94mmol), after completion of dropwise addition, is further stirred 2 hours in 25 DEG C.Add into obtained reactant mixture Enter 2.48g (17.92mmol) 2,5- 4-dihydroxy benzaldehydes and 0.04g (0.36mmol) 4- (dimethylamino) pyridine, again Reactor is impregnated in water-bath and makes temperature in reaction solution be 15 DEG C, with three second that 0.44g (4.30mmol) is added dropwise for 5 minutes Amine.After completion of dropwise addition, all the elements thing is further stirred 2 hours in 25 DEG C.After the completion of reaction, added into reaction solution 300ml distilled water and 50ml saturated aqueous common salt, with 100ml ethyl acetate extraction 2 times.By organic layer anhydrous sodium sulfate After drying, sodium sulphate is filtered out.After filtrate is concentrated with rotary evaporator, 100ml toluene is added into concentrate, passes through filtering Remove the solid of insoluble component.After filtrate is concentrated with rotary evaporator, concentrate is passed through into silica gel column chromatography (THF:Toluene =5:95) purify, thus obtain 0.80g intermediate W1 with 41% yield as white solid.
The structure of object passes through1H-NMR is identified.
1H-NMR(500MHz,CDCl3,TMS,δppm)：10.91 (s, 1H), 9.86 (s, 1H), 7.32 (d, 1H, J= 3.0Hz), 7.25 (dd, 1H, J=3.0Hz, 9.0Hz), 7.01 (d, 1H, J=9.0Hz), 6.97 (d, 2H, J=9.0Hz), 6.87 (d, 2H, J=9.0Hz), 6.40 (dd, 1H, J=1.5Hz, 17.5Hz), 6.12 (dd, 1H, J=10.0Hz, 17.5Hz), 5.82 (dd, 1H, J=1.5Hz, 10.0Hz), 4.17 (t, 2H, J=6.5Hz), 3.94 (t, 2H, J=6.5Hz), 2.53-2.65 (m,2H)、2.23-2.35(m,4H)、1.75-1.84(m,2H)、1.62-1.75(m,6H)、1.41-1.55(m,4H)。
Step 2：The synthesis of intermediate X 1
[changing 123]
In the three neck reactors for possessing thermometer, by 0.87g (2.09mmol) in above-described embodiment in nitrogen stream The intermediate U1 synthesized in the step 1 that 45 compound 32 is synthesized is dissolved in 30ml THF.0.25g is added thereto The mesyl chloride of (2.16mmol), reactor is impregnated in water-bath and makes temperature in reaction solution be 15 DEG C, further with 5 minutes 0.23g (2.23mmol) triethylamine is added dropwise.After completion of dropwise addition, all the elements thing is further stirred 2 hours in 25 DEG C.To In obtained reactant mixture add 0.02g (0.14mmol) 4- (dimethylamino) pyridine, 0.75g (1.39mmol) upper The intermediate W1 synthesized in step 1 is stated, reactor is impregnated in water-bath again and makes temperature in reaction solution be 15 DEG C, with 5 points 0.17g (1.67mmol) triethylamine is added dropwise in clock, after completion of dropwise addition, is further stirred 2 hours in 25 DEG C.Terminate in reaction Afterwards, 200ml distilled water and 20ml saturated aqueous common salt are added into reaction solution, is extracted 2 times with 100ml chloroform.Will be organic After layer anhydrous sodium sulfate drying, sodium sulphate is filtered out.After filtrate is concentrated with rotary evaporator, 100ml is added into concentrate Methanol, the solid of leaching insoluble component.After obtained solid is cleaned with methanol, vacuum drying, as white solid with 75% yield obtains 0.98g intermediate X 1.
The structure of object passes through1H-NMR is identified.
1H-NMR(500MHz,CDCl3,TMS,δppm)：10.09 (s, 1H), 7.61 (d, 1H, J=3.0Hz), 7.36 (dd, 1H, J=3.0Hz, 9.0Hz), 7.21 (d, 1H, J=9.0Hz), 6.97 (d, 2H, J=9.0Hz), 6.97 (d, 2H, J= 9.0Hz), 6.87 (d, 2H, J=9.0Hz), 6.87 (d, 2H, J=9.0Hz), 6.40 (dd, 1H, J=1.5Hz, 17.5Hz), 6.40 (dd, 1H, J=1.5Hz, 17.5Hz), 6.12 (dd, 1H, J=10.0Hz, 17.5Hz), 6.12 (dd, 1H, J= 10.0Hz, 17.5Hz), 5.82 (dd, 1H, J=1.5Hz, 10.0Hz), 5.82 (dd, 1H, J=1.5Hz, 10.0Hz), 4.17 (t, 2H, J=6.5Hz), 4.17 (t, 2H, J=6.5Hz), 3.94 (t, 2H, J=6.5Hz), 3.94 (t, 2H, J=6.5Hz), 2.77-2.93(m,2H)、2.52-2.66(m,2H)、2.09-2.37(m,8H)、1.85-2.04(m,4H)、1.58-1.84(m, 12H)、1.38-1.56(m,8H)。
Step 3：The synthesis of compound 33
In the three neck reactors for possessing thermometer, by the intermediate X 1 synthesized in step 2 above in nitrogen stream： 0.94g (1.00mmol) is dissolved in 15ml THF.Into the solution add 0.20ml (0.20mmol) 1N hydrochloric acid and The intermediate J synthesized in the step 1 that 0.37g (1.49mmol) compound 4 in above-described embodiment 4 is synthesized, by all the elements Thing is stirred 10 hours in 60 DEG C.After the completion of reaction, reaction solution is concentrated with rotary evaporator, concentrate is passed through into silicagel column color Spectrometry (chloroform:THF=98:2) purify, thus obtain 0.92g compound 33 with 79% yield as faint yellow solid.
The structure of object passes through1H-NMR is identified.
1H-NMR(500MHz,CDCl3,TMS,δppm)：7.74 (d, 1H, J=2.5Hz), 7.64-7.71 (m, 3H), 7.33 (dt, 1H, J=1.0Hz, 7.5Hz), 7.07-7.19 (m, 3H), 6.99 (d, 2H, J=9.0Hz), 6.96 (d, 2H, J= 9.0Hz), 6.88 (d, 2H, J=9.0Hz), 6.87 (d, 2H, J=9.0Hz), 6.40 (dd, 1H, J=1.5Hz, 17.5Hz), 6.39 (dd, 1H, J=1.5Hz, 17.5Hz), 6.13 (dd, 1H, J=10.5Hz, 17.5Hz), 6.11 (dd, 1H, J= 10.5Hz, 17.5Hz), 5.82 (dd, 1H, J=1.5Hz, 10.5Hz), 5.81 (dd, 1H, J=1.5Hz, 10.5Hz), 4.28 (t, 2H, J=7.5Hz), 4.17 (t, 2H, J=6.5Hz), 4.16 (t, 2H, J=6.5Hz), 3.90-3.97 (m, 4H), 2.80- 2.88(m,2H)、2.54-2.71(m,2H)、2.26-2.38(m,4H)、2.09-2.26(m,4H)、1.85-2.03(m,4H)、 1.64-1.83 (m, 14H), 1.24-1.55 (m, 14H), 0.87 (t, 3H, J=7.0Hz).
<The measure 2 of phase transition temperature>
10mg compound obtained above 9~33 is weighed respectively, directly with solid state, is sandwiched in 2 and was implemented grinding In the glass substrate with alignment film of polyimide of processing.The substrate is placed on hot plate, 250 DEG C are warming up to from 40 DEG C Afterwards, 40 DEG C are cooled to again.With the change of institutional framework during polarized light microscope observing heating, cooling.
The phase transition temperature of measure is illustrated in following table 3.
[table 3]
Table 3
[table 4]
The (Continued) of table 3
(embodiment 47,48)
By the respectively 1.0g compound 9 obtained in embodiment 22,23,10,30mg Photoepolymerizationinitiater initiater A, 1% cyclopentanone solution of 100mg surfactant A is dissolved in 2.3g cyclopentanone, 2.26g chloroform.The solution is used Disposable filter filtering with 0.45 μm of micropore diameter, obtains polymerizable composition, polymerizable composition 14,15.
(embodiment 49)
The 1.0g compound 11 obtained in embodiment 24,30mg Photoepolymerizationinitiater initiater A, 100mg surface are lived Property agent A 1% cyclopentanone solution is dissolved in 2.3g cyclopentanone.The solution is used with the disposable of 0.45 μm of micropore diameter Filter is filtered, and obtains polymerizable composition, polymerizable composition 16.
(embodiment 50)
The 1.0g compound 12 obtained in embodiment 25,30mg Photoepolymerizationinitiater initiater A, 100mg surface are lived Property agent A 1% cyclopentanone solution is dissolved in 2.3g cyclopentanone, 1.7g chloroform.The solution is used micro- with 0.45 μm The disposable filter filtering in aperture, obtains polymerizable composition, polymerizable composition 17.
(embodiment 51)
The 1.0g compound 13 obtained in embodiment 26,30mg Photoepolymerizationinitiater initiater A, 100mg surface are lived Property agent A 1% cyclopentanone solution is dissolved in 2.3g cyclopentanone.The solution is used with the disposable of 0.45 μm of micropore diameter Filter is filtered, and obtains polymerizable composition, polymerizable composition 18.
(embodiment 52)
The 1.0g compound 14 obtained in embodiment 27,30mg Photoepolymerizationinitiater initiater A, 100mg surface are lived Property agent A 1% cyclopentanone solution is dissolved in 2.3g cyclopentanone, 1.7g chloroform.The solution is used micro- with 0.45 μm The disposable filter filtering in aperture, obtains polymerizable composition, polymerizable composition 19.
(embodiment 53,54)
By the respectively 1.0g compound 15 obtained in embodiment 28,16,30mg Photoepolymerizationinitiater initiater A, 100mg 1% cyclopentanone solution of surfactant A be dissolved in 2.3g cyclopentanone.The solution is used with 0.45 μm of micropore diameter Disposable filter filtering, obtain polymerizable composition, polymerizable composition 20,21.
(embodiment 55)
The light of the 0.5g compound 17 obtained in embodiment 30, the compound 4 of 0.5g embodiment 4,30mg is gathered Initiator A, 1% cyclopentanone solution of 100mg surfactant A is closed to be dissolved in 3.26g chloroform.By the solution with having The disposable filter filtering of 0.45 μm of micropore diameter, obtains polymerizable composition, polymerizable composition 22.
(embodiment 56~63)
By the respectively 1.0g compound 18~25 obtained in embodiment 31,30mg Photoepolymerizationinitiater initiater A, 1% cyclopentanone solution of 100mg surfactant A is dissolved in 2.3g cyclopentanone.The solution is used with 0.45 μm The disposable filter filtering of micropore diameter, obtains polymerizable composition, polymerizable composition 23~30.
(embodiment 64)
The 1.0g compound 26 obtained in embodiment 39,30mg Photoepolymerizationinitiater initiater A, 100mg surface are lived Property agent A 1% cyclopentanone solution is dissolved in 2.3g cyclopentanone, 0.7g chloroform.The solution is used micro- with 0.45 μm The disposable filter filtering in aperture, obtains polymerizable composition, polymerizable composition 31.
(embodiment 65)
The 1.0g compound 27 obtained in embodiment 40,30mg Photoepolymerizationinitiater initiater A, 100mg surface are lived Property agent A 1% cyclopentanone solution is dissolved in 2.3g cyclopentanone.The solution is used with the disposable of 0.45 μm of micropore diameter Filter is filtered, and obtains polymerizable composition, polymerizable composition 32.
(embodiment 66)
The 1.0g compound 28 obtained in embodiment 41,30mg Photoepolymerizationinitiater initiater A, 100mg surface are lived Property agent A 1% cyclopentanone solution is dissolved in 2.3g cyclopentanone, 0.7g chloroform.The solution is used micro- with 0.45 μm The disposable filter filtering in aperture, obtains polymerizable composition, polymerizable composition 33.
(embodiment 67,68)
By the respectively 1.0g compound 29 obtained in embodiment 42,43,30,30mg Photoepolymerizationinitiater initiater A, 1% cyclopentanone solution of 100mg surfactant A is dissolved in 2.3g cyclopentanone.The solution is used with 0.45 μm The disposable filter filtering of micropore diameter, obtains polymerizable composition, polymerizable composition 34,35.
(embodiment 69)
The 1.0g compound 31 obtained in embodiment 44,30mg Photoepolymerizationinitiater initiater A, 100mg surface are lived Property agent A 1% cyclopentanone solution is dissolved in 2.3g cyclopentanone, 0.7g chloroform.The solution is used micro- with 0.45 μm The disposable filter filtering in aperture, obtains polymerizable composition, polymerizable composition 36.
(embodiment 70,71)
The respectively 0.3g compound 32 obtained in embodiment 44,45,33,0.7g are obtained in example 4 Compound 4,1% cyclopentanone solution of 30mg Photoepolymerizationinitiater initiater A, 100mg surfactant A is dissolved in 2.3g ring In pentanone.Use the disposable filter with 0.45 μm of micropore diameter to filter the solution, respectively obtain polymerizable composition, polymerizable composition 37, 38。
Obtained polymerizable composition, polymerizable composition 14~38 is polymerize by following method to obtain macromolecule.For obtained height Molecule, carries out the measure of phase difference and the evaluation of wavelength dispersion respectively.
<The measure of phase difference and the evaluation II of wavelength dispersion>
(i) formation 1 of the liquid crystal layer of polymerizable composition, polymerizable composition is used
In being provided with the transparent glass substrate of alignment film of polyimide for ground processing, it is coated with respectively using #4 bars Polymerizable composition, polymerizable composition 16~18,20~30,32 and 34~38.After film is dried 1 minute at the temperature shown in following table 4, Orientation process 1 minute at the temperature shown in table 4, forms liquid crystal layer.Then, the coating surface side from liquid crystal layer is shown in table 4 At a temperature of irradiate 2000mJ/cm2Ultraviolet polymerize, wavelength dispersion test sample is made.
(ii) formation 2 of the liquid crystal layer of polymerizable composition, polymerizable composition is used
In being provided with the transparent glass substrate of alignment film of polyimide for ground processing, it is coated with respectively using #6 bars Polymerizable composition, polymerizable composition 14,15,19,31 and 33.After film is dried 1 minute at the temperature shown in following table 4, shown in table 4 At a temperature of orientation process 1 minute, form liquid crystal layer.Then, irradiated from the coating surface side of liquid crystal layer at the temperature shown in table 4 2000mJ/cm2Ultraviolet polymerize, wavelength dispersion test sample is made.
(iii) measure of phase difference, the evaluation of wavelength dispersion
For obtained sample, pass through the measure of method progress phase difference same as described above, the evaluation of wavelength dispersion.
By the film thickness (μm) of liquid crystal liquid crystal property polymeric membrane obtained from polymerization, the phase difference (Re) of 548.5nm wavelength, α, β Value collect and be illustrated in following table 4.
As shown in Table 4, the macromolecule of the embodiment 47~71 obtained using compound 9~33 involved in the present invention is light Learn anisotropic body.In addition, the α of obtained optically anisotropic body, which is less than 1, β, is more than 1 or about 1, broadband is presented in display The preferable wavelength dispersibility of property.
(embodiment 72) compound 34
[changing 124]
Step 1：Intermediate Y1 synthesis
[changing 125]
In possessing four neck reactors of thermometer, by 2.50g (15.1mmol) 2- diazanyl benzo thiophenes in nitrogen stream Azoles is dissolved in 20ml DMF.7.38g (22.7mmol) cesium carbonate, 2.45g (18.2mmol) 3- is added into the solution Bromo- 2- methyl-1-propylenes, all the elements thing is stirred 18 hours in 25 DEG C.After the completion of reaction, by reaction solution put into In 200ml water, with 300ml ethyl acetate extraction.After ethyl acetate layer anhydrous sodium sulfate drying, sodium sulphate is filtered out. Ethyl acetate is distilled off from filtrate decompression with rotary evaporator, yellow solid is obtained.The yellow solid is passed through into silicagel column color Spectrometry (hexane:Ethyl acetate=80:20) purify, 368mg intermediate Y1 (yields are obtained as white solid：11.1%).
The structure of object passes through1H-NMR is identified.
1H-NMR(500MHz,CDCl3,TMS,δppm)：7.59 (dd, 1H, J=1.0Hz, 8.0Hz), 7.52 (dd, 1H, J =1.5Hz, 8.0Hz), 7.26 (ddd, 1H, J=1.0Hz, 7.5Hz, 8.0Hz), 7.05 (ddd, 1H, J=1.5Hz, 7.5Hz, 8.0Hz)、4.98(s,1H)、4.86(s,1H)、4.29(s,2H)、4.12(s,2H)、1.71(s,3H)。
Step 2：The synthesis of compound 34
In possessing four neck reactors of thermometer, in nitrogen stream by 368mg (1.68mmol) in above-mentioned steps 1 The intermediate B synthesized in the step 2 that the intermediate Y1 and 1.0g (1.06mmol) of the synthesis compound 1 in embodiment 1 are synthesized It is dissolved in 3ml ethanol and 15ml THF in the mixed solvent.Into the solution add 49.2mg (0.21mmol) (±)- 10- camphorsulfonic acids, all the elements thing is stirred 5 hours in 40 DEG C.After the completion of reaction, reaction solution is put into 150ml water In, with 300ml ethyl acetate extraction.After ethyl acetate layer anhydrous sodium sulfate drying, sodium sulphate is filtered out.Use rotary evaporation Ethyl acetate is distilled off from filtrate decompression in device, obtains yellow solid.The yellow solid is passed through into silica gel column chromatography (toluene: Ethyl acetate=90:10) purify, the 1.07g (yield of compound 34 is obtained as white solid：88.5%).
The structure of object passes through1H-NMR is identified.
1H-NMR(500MHz,CDCl3,TMS,δppm)：7.74 (d, 1H, J=2.5Hz), 7.70 (d, 1H, J=7.5Hz), 7.67 (d, 1H, J=8.0Hz), 7.63 (s, 1H), 7.34 (dd, 1H, J=7.5Hz, 8.0Hz), 7.18 (dd, 1H, J= 7.5Hz, 7.5Hz), 7.12 (d, 1H, J=9.0Hz), 7.10 (dd, 1H, J=2.5Hz, 9.0Hz), 6.99 (d, 2H, J= 9.0Hz), 6.98 (d, 2H, J=9.0Hz), 6.88 (d, 4H, J=9.0Hz), 6.40 (dd, 2H, J=1.5Hz, 17.5Hz), 6.13 (dd, 2H, J=10.5Hz, 17.5Hz), 5.82 (dd, 2H, J=1.5Hz, 10.5Hz), 4.98 (s, 1H), 4.90 (s, 2H), 4.83 (s, 1H), 4.18 (t, 4H, J=6.5Hz), 3.95 (t, 4H, J=6.5Hz), 2.56-2.66 (m, 4H), 2.31- 2.36(m,8H)、1.76-1.82(m,7H)、1.64-1.74(m,12H)、1.40-1.55(m,8H)。
(embodiment 73) compound 35
[changing 126]
Step 1：Intermediate Z1 synthesis
[changing 127]
In possessing four neck reactors of thermometer, by 5.00g (30.3mmol) 2- diazanyl benzo thiophenes in nitrogen stream Azoles is dissolved in 50ml DMF.14.8g (45.5mmol) cesium carbonate, 4.98g (36.4mmol) 1- is added into the solution Bromo- 2- methylpropanes, all the elements thing is stirred 24 hours in 25 DEG C.After the completion of reaction, reaction solution is put into 200ml's In water, with 300ml ethyl acetate extraction.After ethyl acetate layer anhydrous sodium sulfate drying, sodium sulphate is filtered out.Steamed with rotation Ethyl acetate is distilled off from filtrate decompression in hair device, obtains yellow solid.By the yellow solid by silica gel column chromatography (just oneself Alkane:Ethyl acetate=85:15) purify, 3.28g intermediate Z1 (yields are obtained as white solid：48.9%).
The structure of object passes through1H-NMR is identified.
1H-NMR(500MHz,CDCl3,TMS,δppm)：7.60 (dd, 1H, J=1.0Hz, 7.5Hz), 7.52 (dd, 1H, J =1.0Hz, 8.5Hz), 7.27 (ddd, 1H, J=1.0Hz, 7.5Hz, 8.5Hz), 7.06 (ddd, 1H, J=1.0Hz, 7.5Hz, 7.5Hz), 4.24 (s, 2H), 3.57 (d, 2H, J=6.5Hz), 2.14-2.25 (triplet of septets, 1H, J= 6.5Hz, 6.5Hz), 1.00 (d, 6H, J=6.5Hz).
Step 2：The synthesis of compound 35
In possessing four neck reactors of thermometer, in nitrogen stream by 518mg (2.34mmol) in above-mentioned steps 1 The intermediate B synthesized in the step 2 that the intermediate Z1 and 2.00g (2.12mmol) of the synthesis compound 1 in embodiment 1 are synthesized It is dissolved in 3ml ethanol and 20ml THF in the mixed solvent.Into the solution add 54.4mg (0.24mmol) (±)- 10- camphorsulfonic acids, all the elements thing is stirred 7 hours in 40 DEG C.After the completion of reaction, reaction solution is put into 150ml water In, with 300ml ethyl acetate extraction.After ethyl acetate layer anhydrous sodium sulfate drying, sodium sulphate is filtered out.Use rotary evaporation Ethyl acetate is distilled off from filtrate decompression in device, obtains yellow solid.The yellow solid is passed through into silica gel column chromatography (toluene: Ethyl acetate=90:10) purify, the 1.83g (yield of compound 35 is obtained as white solid：75.7%).
The structure of object passes through1H-NMR is identified.
1H-NMR(500MHz,CDCl3,TMS,δppm)：7.76 (d, 1H, J=2.5Hz), 7.692 (s, 1H), 7.690 (d, 1H, J=7.5Hz), 7.66 (d, 1H, J=8.0Hz), 7.34 (dd, 1H, J=7.5Hz, 8.0Hz), 7.17 (dd, 1H, J= 7.5Hz, 7.5Hz), 7.12 (d, 1H, J=9.0Hz), 7.10 (dd, 1H, J=2.5Hz, 9.0Hz), 6.99 (d, 2H, J= 9.0Hz), 6.98 (d, 2H, J=9.0Hz), 6.88 (d, 4H, J=9.0Hz), 6.40 (dd, 2H, J=1.5Hz, 17.5Hz), 6.13 (dd, 2H, J=10.5Hz, 17.5Hz), 5.82 (dd, 2H, J=1.5Hz, 10.5Hz), 4.16-4.19 (m, 6H), 3.95 (t, 4H, J=6.5Hz), 2.59-2.68 (m, 4H), 2.23-2.35 (m, 9H), 1.76-1.82 (m, 4H), 1.66-1.74 (m, 12H), 1.42-1.54 (m, 8H), 1.03 (d, 6H, J=6.5Hz).
(embodiment 74) compound 36
[changing 128]
Step 1：The synthesis of intermediate A 2
[changing 129]
In possessing four neck reactors of thermometer, by 2.50g (15.1mmol) 2- diazanyl benzo thiophenes in nitrogen stream Azoles is dissolved in 20ml DMF.7.38g (22.7mmol) cesium carbonate, 4.17g (18.2mmol) 2- is added into the solution Bromomethyl-Isosorbide-5-Nitrae-benzodioxan, all the elements thing is stirred 6 hours in 25 DEG C.After the completion of reaction, by reaction solution put into In 200ml water, with 300ml ethyl acetate extraction.After ethyl acetate layer anhydrous sodium sulfate drying, sodium sulphate is filtered out. Ethyl acetate is distilled off from filtrate decompression with rotary evaporator, yellow solid is obtained.The yellow solid is passed through into silicagel column color Spectrometry (n-hexane:Ethyl acetate=70:30) purify, the 2.39g (yield of intermediate A 2 is obtained as white solid： 53.7%).
The structure of object passes through1H-NMR is identified.
1H-NMR(500MHz,CDCl3,TMS,δppm)：7.62 (dd, 1H, J=1.0Hz, 8.0Hz), 7.51 (dd, 1H, J =1.0Hz, 8.0Hz), 7.28 (ddd, 1H, J=1.0Hz, 7.5Hz, 8.0Hz), 7.08 (ddd, 1H, J=1.0Hz, 7.5Hz, 8.0Hz), 6.83-6.90 (m, 4H), 4.72 (dddd, 1H, J=2.5Hz, 3.0Hz, 7.0Hz, 7.0Hz), 4.64 (s, 2H), 4.39 (dd, 1H, J=2.5Hz, 12.5Hz), 4.25 (dd, 1H, J=3.0Hz, 15.0Hz), 4.07 (dd, 1H, J=7.0Hz, 12.0Hz), 3.98 (dd, 1H, J=7.0Hz, 15.0Hz).
Step 2：The synthesis of compound 36
In possessing four neck reactors of thermometer, in nitrogen stream by 627mg (2.13mmol) in above-mentioned steps 1 The intermediate B synthesized in the step 2 that the compound 1 in embodiment 1 of the intermediate A 2 and 1.00g (1.06mmol) of synthesis is synthesized It is dissolved in 3ml ethanol and 15ml THF in the mixed solvent.Into the solution add 49.2mg (0.21mmol) (±)- 10- camphorsulfonic acids, all the elements thing is stirred 4 hours in 40 DEG C.After the completion of reaction, reaction solution is put into 150ml water In, with 300ml ethyl acetate extraction.After ethyl acetate layer anhydrous sodium sulfate drying, sodium sulphate is filtered out.Use rotary evaporation Ethyl acetate is distilled off from filtrate decompression in device, obtains yellow solid.The yellow solid is passed through into silica gel column chromatography (toluene: Ethyl acetate=90:10) purify, the 1.11g (yield of compound 36 is obtained as white solid：84.8%).
The structure of object passes through1H-NMR is identified.
1H-NMR(500MHz,CDCl3,TMS,δppm)：8.02 (s, 1H), 7.76 (d, 1H, J=2.0Hz), 7.71 (d, 1H, J=7.5Hz), 7.67 (d, 1H, J=8.0Hz), 7.36 (dd, 1H, J=7.5Hz, 8.0Hz), 7.20 (dd, 1H, J= 7.5Hz, 7.5Hz), 7.13 (dd, 1H, J=2.0Hz, 9.0Hz), 7.11 (d, 1H, J=9.0Hz), 6.99 (d, 2H, J= 9.0Hz), 6.97 (d, 2H, J=9.0Hz), 6.88 (d, 4H, J=9.0Hz), 6.85-6.87 (m, 4H), 6.40 (dd, 2H, J= 1.0Hz, 17.5Hz), 6.13 (dd, 2H, J=10.5Hz, 17.5Hz), 5.82 (dd, 2H, J=1.0Hz, 10.5Hz), 4.75 (dd, 1H, J=6.0Hz, 15.0Hz), 4.68 (dddd, 1H, J=2.0Hz, 5.5Hz, 6.0Hz, 7.0Hz), 4.47 (dd, 1H, J =2.0Hz, 11.5Hz), 4.42 (dd, 1H, J=5.5Hz, 15.0Hz), 4.18 (t, 4H, J=7.0Hz), 4.08 (dd, 1H, J =7.5Hz, 11.5Hz), 3.95 (t, 4H, J=6.0Hz), 2.57-2.68 (m, 3H), 2.41-2.47 (m, 1H), 2.24-2.36 (m,6H)、2.17-2.20(m,2H)、1.77-1.82(m,4H)、1.69-1.74(m,8H)、1.56-1.65(m,4H)、1.42- 1.54(m,8H)。
(embodiment 75) compound 37
[changing 130]
Step 1：The synthesis of intermediate B 2
[changing 131]
In possessing four neck reactors of thermometer, by 5.00g (30.3mmol) 2- diazanyl benzo thiophenes in nitrogen stream Azoles is dissolved in 50ml DMF.Into the solution add 14.8g (45.5mmol) cesium carbonate, 7.30g (36.6mmol) β- Bromoethyl phenyl ether, all the elements thing is stirred 24 hours in 25 DEG C.After the completion of reaction, reaction solution is put into 200ml water, With 300ml ethyl acetate extraction.After ethyl acetate layer anhydrous sodium sulfate drying, sodium sulphate is filtered out.Use rotary evaporator Ethyl acetate is distilled off from filtrate decompression, yellow solid is obtained.The yellow solid is passed through into silica gel column chromatography (n-hexane: Ethyl acetate=70:30) purify, the 2.26g (yield of intermediate B 2 is obtained as white solid：28.1%).
The structure of object passes through1H-NMR is identified.
1H-NMR(500MHz,CDCl3,TMS,δppm)：7.61 (dd, 1H, J=1.0Hz, 7.5Hz), 7.53 (dd, 1H, J =1.0Hz, 8.0Hz), 7.26-7.31 (m, 3H), 7.07 (ddd, 1H, J=1.0Hz, 7.5Hz, 8.0Hz), 6.97 (ddd, 1H, J=1.0Hz, 7.5Hz, 7.5Hz), 6.90 (dd, 2H, J=1.0Hz, 8.5Hz), 4.70 (s, 2H), 4.39 (t, 2H, J= 4.5Hz), 4.23 (t, 2H, J=4.5Hz).
Step 2：The synthesis of compound 37
In possessing four neck reactors of thermometer, in nitrogen stream by 312mg (1.77mmol) in above-mentioned steps 1 The intermediate B synthesized in the step 2 that the compound 1 in embodiment 1 of the intermediate B 2 and 1.00g (1.06mmol) of synthesis is synthesized It is dissolved in 3ml ethanol and 15ml THF in the mixed solvent.Into the solution add 27.1mg (0.12mmol) (±)- 10- camphorsulfonic acids, all the elements thing is stirred 7 hours in 40 DEG C.After the completion of reaction, reaction solution is put into 150ml water In, with 300ml ethyl acetate extraction.After ethyl acetate layer anhydrous sodium sulfate drying, sodium sulphate is filtered out.Use rotary evaporation Ethyl acetate is distilled off from filtrate decompression in device, obtains yellow solid.The yellow solid is passed through into silica gel column chromatography (toluene: Ethyl acetate=90:10) purify, the 1.18g (yield of compound 37 is obtained as white solid：92.3%).
The structure of object passes through1H-NMR is identified.
1H-NMR(500MHz,CDCl3,TMS,δppm)：8.14 (s, 1H), 7.78 (d, 1H, J=1.0Hz), 7.70 (d, 1H, J=8.0Hz), 7.67 (d, 1H, J=8.0Hz), 7.35 (dd, 1H, J=7.5Hz, 8.0Hz), 7.24-7.27 (m, 2H), 7.18 (dd, 1H, J=7.5Hz, 8.0Hz), 7.14 (dd, 1H, J=1.0Hz, 7.5Hz), 7.12 (d, 1H, J=7.5Hz), 6.93-7.00 (m, 5H), 6.87-6.90 (m, 6H), 6.40 (dd, 2H, J=1.5Hz, 17.5Hz), 6.13 (dd, 2H, J= 10.5Hz, 17.5Hz), 5.82 (dd, 2H, J=1.5Hz, 10.5Hz), 4.69 (t, 2H, J=6.0Hz), 4.36 (t, 2H, J= 6.0Hz), 4.17 (t, 4H, J=6.5Hz), 3.95 (t, 2H, J=6.5Hz), 3.94 (t, 2H, J=6.5Hz), 2.56-2.68 (m,3H)、2.31-2.39(m,5H)、2.23-2.27(m,2H)、2.11-2.14(m,2H)、1.77-1.85(m,4H)、1.69- 1.74(m,8H)、1.42-1.65(m,12H)。
(embodiment 76) compound 38
[changing 132]
Step 1：Intermediate C2 synthesis
[changing 133]
In possessing four neck reactors of thermometer, by 2.00g (12.1mmol) 2- diazanyl benzo thiophenes in nitrogen stream Azoles is dissolved in 30ml DMF.7.88g (24.2mmol) cesium carbonate, 3.15g (14.5mmol) 2- is added into the solution Bromoethyl aralkyl sulfid, all the elements thing is stirred 3 hours in 25 DEG C.After the completion of reaction, reaction solution is put into 200ml's In water, with 300ml ethyl acetate extraction, after ethyl acetate layer anhydrous sodium sulfate drying, sodium sulphate is filtered out.Steamed with rotation Ethyl acetate is distilled off from filtrate decompression in hair device, obtains yellow solid.By the yellow solid by silica gel column chromatography (just oneself Alkane:Ethyl acetate=80:20) purify, 1.55g intermediate C2 (yields are obtained as white solid：42.5%).
The structure of object passes through1H-NMR is identified.
1H-NMR(500MHz,CDCl3,TMS,δppm)：7.61 (dd, 1H, J=1.3Hz, 8.0Hz), 7.53 (dd, 1H, J =1.3Hz, 8.0Hz), 7.38-7.43 (m, 2H), 7.27-7.32 (m, 3H), 7.21 (ddd, 1H, J=1.3Hz, 8.0Hz, 8.0Hz), 7.08 (ddd, 1H, J=1.3Hz, 8.0Hz, 8.0Hz), 4.44 (s, 2H), 4.00 (t, 2H, J=6.5Hz), 3.36 (t, 2H, J=6.5Hz).
Step 2：The synthesis of compound 38
In possessing three neck reactors of thermometer, add in nitrogen stream 1.50g (1.60mmol) in embodiment 1 Compound 1 synthesize step 2 in synthesize intermediate B, 534mg (1.78mmol) intermediate synthesized in above-mentioned steps 1 C2,41.4mg (0.178mmol) (±) -10- camphorsulfonic acids, 16ml THF and 4ml ethanol, are made uniform solution, will All the elements thing is stirred 5 hours in 40 DEG C.After the completion of reaction, reaction solution is put into 100ml water, with 200ml chlorine Imitative extraction.After organic layer anhydrous sodium sulfate drying, sodium sulphate is filtered out.After filtrate is concentrated with rotary evaporator, it will concentrate Thing passes through silica gel column chromatography (toluene:Ethyl acetate=9:1) purify, 1.67g compound 38 is obtained as faint yellow solid (yield：86.9%).
The structure of object passes through1H-NMR is identified.
1H-NMR(500MHz,CDCl3,TMS,δppm)：7.74(s,1H)、7.65-7.72(m,3H)、7.44-7.49(m, 2H), 7.30-7.39 (m, 3H), 7.23 (ddd, 1H, J=1.0Hz, 7.0Hz, 7.0Hz), 7.19 (ddd, 1H, J=1.0Hz, 7.0Hz, 7.0Hz), 7.10-7.14 (m, 2H), 6.96-7.01 (m, 4H), 6.86-6.91 (m, 4H), 6.40 (dd, 2H, J= 1.5Hz, 17.5Hz), 6.13 (dd, 2H, J=10.5Hz, 17.5Hz), 5.82 (dd, 2H, J=1.5Hz, 10.5Hz), 5.22 (t, 2H, J=8.0Hz), 4.18 (t, 4H, J=6.5Hz), 3.95 (t, 4H, J=6.5Hz), 3.28 (t, 2H, J=8.0Hz), 2.52-2.73(m,4H)、2.24-2.40(m,8H)、1.62-1.84(m,16H)、1.41-1.56(m,8H)。
(embodiment 77) compound 39
[changing 134]
Step 1：Intermediate D2 synthesis
[changing 135]
In possessing three neck reactors of thermometer, by 2.00g (12.1mmol) 2- diazanyl benzo thiophenes in nitrogen stream Azoles is dissolved in 30ml DMF.7.88g (24.2mol) cesium carbonate is added into the solution and 0 DEG C is cooled to, with 5 minutes drops Plus 2.83g (14.5mmol) 2- (2- bromoethyls) -1,3- dioxanes, after completion of dropwise addition, reaction solution is recovered to 25 DEG C simultaneously Stirring 25 hours.After the completion of reaction, 200ml water is added into reaction solution, with 100ml ethyl acetate extraction 2 times.To have After machine layer anhydrous sodium sulfate drying, sodium sulphate is filtered out.After filtrate is concentrated with rotary evaporator, obtained white solid is used 50ml toluene cleaning, by being dried in vacuo so as to obtain 1.45g intermediate D2 (yield 42.9%) as white solid.
The structure of object passes through1H-NMR is identified.
1H-NMR(400MHz,CDCl3,TMS,δppm)：7.59 (dd, 1H, J=1.3Hz, 7.5Hz), 7.52 (dd, 1H, J =1.3Hz, 7.5Hz), 7.27 (ddd, 1H, J=1.3Hz, 7.5Hz, 7.5Hz), 7.05 (ddd, 1H, J=1.3Hz, 7.5Hz, 7.5Hz), 4.70 (t, 1H, J=4.5Hz), 4.47 (s, 2H), 4.00-4.12 (m, 2H), 3.93 (t, 2H, J=6.5Hz), 3.68-3.76(m,2H)、1.98-2.11(m,3H)、1.29-1.36(m,1H)。
Step 2：The synthesis of compound 39
Add into the three neck reactors for possess thermometer in nitrogen stream 1.50g (1.60mmol) in embodiment 1 Compound 1 synthesize step 2 in synthesize intermediate B, 495mg (1.78mmol) intermediate synthesized in above-mentioned steps 1 D2,41.4mg (0.178mmol) (±) -10- camphorsulfonic acids, 16ml THF and 4ml ethanol, are made uniform solution, will All the elements thing is stirred 3 hours in 40 DEG C.After the completion of reaction, reaction solution is put into 100ml water, with 200ml chlorine Imitative extraction.After organic layer anhydrous sodium sulfate drying, sodium sulphate is filtered out.After filtrate is concentrated with rotary evaporator, it will concentrate Thing passes through silica gel column chromatography (toluene:Ethyl acetate=92:8) purify, 1.61g compound 39 is obtained as faint yellow solid (yield：83.8%).
The structure of object passes through1H-NMR is identified.
1H-NMR(500MHz,CDCl3,TMS,δppm)：7.79 (s, 1H), 7.74 (d, 1H, J=1.5Hz), 7.69 (dd, 1H, J=1.3Hz, 6.5Hz), 7.67 (dd, 1H, J=1.3Hz, 6.5Hz), 7.34 (ddd, 1H, J=1.3Hz, 6.5Hz, 6.5Hz), 7.16 (ddd, 1H, J=1.3Hz, 6.5Hz, 6.5Hz), 7.08-7.13 (m, 2H), 6.95-7.01 (m, 4H), 6.85-6.91 (m, 4H), 6.40 (dd, 2H, J=1.5Hz, 17.5Hz), 6.13 (dd, 2H, J=10.5Hz, 17.5Hz), 5.82 (dd, 2H, J=1.5Hz, 10.5Hz), 4.68 (t, 1H, J=5.0Hz), 4.41 (t, 2H, J=7.5Hz), 4.18 (t, 4H, J= 6.5Hz), 4.07-4.14 (m, 2H), 3.94 (t, 4H, J=6.5Hz), 3.71-3.79 (m, 2H), 2.55-2.75 (m, 4H), 2.25-2.41(m,8H)、2.01-2.15(m,3H)、1.64-1.84(m,16H)、1.41-1.56(m,8H)、1.32-1.38(m, 1H)。
(embodiment 78) compound 40
[changing 136]
Step 1：The synthesis of intermediate E 2
[changing 137]
In possessing three neck reactors of thermometer, by 2.00g (12.1mmol) 2- diazanyl benzo thiophenes in nitrogen stream Azoles is dissolved in 30ml DMF.7.88g (24.2mol) cesium carbonate is added into the solution and 0 DEG C is cooled to, with 5 minutes drops Plus 2.42g (14.5mmol) 2- bromomethyl DOXs, it is after completion of dropwise addition, all the elements thing is further in 25 DEG C Stirring 3 hours.After the completion of reaction, 200ml water is added into reaction solution, with 100ml ethyl acetate extraction 2 times.To have After machine layer anhydrous sodium sulfate drying, sodium sulphate is filtered out.After filtrate is concentrated with rotary evaporator, concentrate is passed through into silicagel column Chromatography (n-hexane:Ethyl acetate=55:45) purify, the 1.31g (yield of intermediate E 2 is thus obtained as white solid： 43.1%).
The structure of object passes through1H-NMR is identified.
1H-NMR(500MHz,CDCl3,TMS,δppm)：7.60 (dd, 1H, J=1.0Hz, 7.5Hz), 7.53 (dd, 1H, J =1.0Hz, 7.5Hz), 7.27 (ddd, 1H, J=1.0Hz, 7.5Hz, 7.5Hz), 7.06 (ddd, 1H, J=1.0Hz, 7.5Hz, 7.5Hz), 5.19 (t, 1H, J=4.5Hz), 4.63 (s, 2H), 3.93-4.05 (m, 4H), 3.86-3.94 (m, 2H).
Step 2：The synthesis of compound 40
Add into the three neck reactors for possess thermometer in nitrogen stream 1.50g (1.60mmol) in embodiment 1 Compound 1 synthesize step 2 in synthesize intermediate B, 447mg (1.78mmol) intermediate synthesized in above-mentioned steps 1 E2,41.4mg (0.178mmol) (±) -10- camphorsulfonic acids, 16ml THF and 4ml ethanol, are made uniform solution.So Afterwards, all the elements thing is stirred 5 hours in 40 DEG C.After the completion of reaction, reaction solution is put into 100ml water, uses 200ml Chloroform extraction.After organic layer is dried with sodium sulphate, concentrated with rotary evaporator, then pass through silica gel column chromatography (toluene: Ethyl acetate=85:15) purify, the 1.60g (yield of compound 40 is obtained as faint yellow solid：85.7%).
The structure of object passes through1H-NMR is identified.
1H-NMR(500MHz,CDCl3,TMS,δppm)：8.11 (s, 1H), 7.76 (d, 1H, J=1.5Hz), 7.71 (dd, 1H, J=1.0Hz, 7.5Hz), 7.69 (dd, 1H, J=1.0Hz, 7.5Hz), 7.39 (ddd, 1H, J=1.0Hz, 7.5Hz, 7.5Hz), 7.17 (ddd, 1H, J=1.0Hz, 7.5Hz, 7.5Hz), 7.09-7.13 (m, 2H), 6.96-7.01 (m, 4H), 6.86-6.91 (m, 4H), 6.40 (dd, 2H, J=1.5Hz, 17.5Hz), 6.13 (dd, 2H, J=10.5Hz, 17.5Hz), 5.82 (dd, 2H, J=1.5Hz, 10.5Hz), 5.24 (t, 1H, J=3.5Hz), 4.57 (d, 2H, J=3.5Hz), 4.18 (t, 4H, J= 6.5Hz), 3.97-4.01 (m, 2H), 3.95 (t, 4H, J=6.5Hz), 3.86-3.90 (m, 2H), 2.55-2.74 (m, 4H), 2.25-2.41(m,8H)、1.64-1.84(m,16H)、1.40-1.55(m,8H)。
(embodiment 79) compound 41
[changing 138]
Step 1：Intermediate F2 synthesis
[changing 139]
In possessing four neck reactors of thermometer, by 2.00g (12.1mmol) 2- diazanyl benzo thiophenes in nitrogen stream Azoles is dissolved in 30ml DMF.7.88g (24.2mmol) cesium carbonate, 5.00g (14.5mmol) 2- is added into the solution (nine fluorine butyl) ethyl iodide, all the elements thing is stirred 20 hours in 25 DEG C.After the completion of reaction, by reaction solution put into In 200ml water, with 300ml ethyl acetate extraction, after ethyl acetate layer anhydrous sodium sulfate drying, sodium sulphate is filtered out. Ethyl acetate is distilled off from filtrate decompression with rotary evaporator, brown solid is obtained.The brown solid is passed through into silicagel column color Spectrometry (n-hexane:Ethyl acetate=9:1) purify, 1.15g intermediate F2 (yields are obtained as white solid：22.9%).
The structure of object passes through1H-NMR is identified.
1H-NMR(500MHz,CDCl3,TMS,δppm)：7.63 (dd, 1H, J=1.0Hz, 7.5Hz), 7.57 (dd, 1H, J =1.0Hz, 7.5Hz), 7.32 (ddd, 1H, J=1.0Hz, 7.5Hz, 7.5Hz), 7.11 (ddd, 1H, J=1.0Hz, 7.5Hz, 7.5Hz), 4.35 (s, 2H), 4.08 (t, 2H, J=7.5Hz), 2.56-2.70 (m, 2H).
Step 2：The synthesis of compound 41
Add into the three neck reactors for possess thermometer in nitrogen stream 1.35g (1.44mmol) in embodiment 1 Compound 1 synthesize step 2 in synthesize intermediate B, 654mg (1.59mmol) intermediate synthesized in above-mentioned steps 1 F2,38.4mg (0.165mmol) (±) -10- camphorsulfonic acids, 16ml THF and 4ml ethanol, are made uniform solution, will All the elements thing is stirred 5 hours in 40 DEG C.After the completion of reaction, reaction solution is put into 100ml water, with 200ml chlorine Imitative extraction.After organic layer anhydrous sodium sulfate drying, sodium sulphate is filtered out.After filtrate is concentrated with rotary evaporator, it will concentrate Thing passes through silica gel column chromatography (toluene:Ethyl acetate=92:8) purify, 1.41g compound 41 is obtained as faint yellow solid (yield：73.6%).
The structure of object passes through1H-NMR is identified.
1H-NMR(500MHz,CDCl3,TMS,δppm)：7.74-7.78(m,2H)、7.69-7.73(m,2H)、7.38 (ddd, 1H, J=1.0Hz, 7.5Hz, 7.5Hz), 7.21 (ddd, 1H, J=1.0Hz, 7.5Hz, 7.5Hz), 7.11-7.17 (m, 2H), 6.95-7.01 (m, 4H), 6.85-6.91 (m, 4H), 6.40 (dd, 2H, J=1.5Hz, 17.5Hz), 6.13 (dd, 2H, J =10.0Hz, 17.5Hz), 5.82 (dd, 2H, J=1.5Hz, 10.0Hz), 4.61-4.69 (m, 2H), 4.18 (t, 4H, J= 6.5Hz), 3.95 (t, 4H, J=6.5Hz), 2.52-2.71 (m, 6H), 2.25-2.40 (m, 8H), 1.61-1.84 (m, 16H), 1.41-1.55(m,8H)。
(embodiment 80) compound 42
[changing 140]
Step 1：Intermediate G2 synthesis
[changing 141]
In possessing three neck reactors of thermometer, by 2.00g (12.11mol) 2- diazanyl benzo thiophenes in nitrogen stream Azoles is dissolved in 40ml DMF.7.89g (24.21mol) cesium carbonate and 1.95g (14.53mmol) is added into the solution 3- bromopropionitriles, all the elements thing is stirred 15 hours in 25 DEG C.After the completion of reaction, 500ml distillation is added into reaction solution Water, with 100ml ethyl acetate extraction 2 times.After organic layer anhydrous sodium sulfate drying, sodium sulphate is filtered out.By filtrate rotation Turn after evaporator concentration, 20ml toluene is added into concentrate and 0 DEG C is cooled to.The crystallization that leaching is separated out, vacuum drying, by This obtains 1.12g intermediate G2 as white solid with 42% yield.
The structure of object passes through1H-NMR is identified.
1H-NMR(500MHz,DMSO-d6,TMS,δppm)：7.70 (dd, 1H, J=1.0Hz, 8.0Hz), 7.42 (dd, 1H, J=1.0Hz, 8.0Hz), 7.24 (dt, 1H, J=1.0Hz, 7.5Hz), 7.03 (dt, 1H, J=1.0Hz, 7.5Hz), 5.47 (s, 2H), 3.99 (t, 2H, J=6.5Hz), 2.97 (t, 2H, J=6.5Hz).
Step 2：The synthesis of compound 42
In possessing three neck reactors of thermometer, by 1.0g (1.06mmol) change in embodiment 1 in nitrogen stream The intermediate B synthesized in the step 2 that compound 1 is synthesized is dissolved in 30ml THF.0.44ml is added into the solution The intermediate G2 synthesized in above-mentioned steps 1 of the 1N hydrochloric acid and 1.12g (5.13mmol) of (0.44mmol), by all the elements thing Stirred 20 hours in 60 DEG C.After the completion of reaction, reaction solution is concentrated with rotary evaporator, concentrate is then passed through into silicagel column Chromatography (chloroform:THF=40:1) purify, thus obtain 0.55g compound 42 with 91% yield as faint yellow solid.
The structure of object passes through1H-NMR is identified.
1H-NMR(500MHz,CDCl3,TMS,δppm)：7.84(s,1H)、7.66-7.76(m,3H)、7.38(dt,1H,J =1.0Hz, 7.5Hz), 7.22 (dt, 1H, J=1.0Hz, 7.5Hz), 7.13-7.16 (m, 2H), 6.99 (d, 2H, J= 9.0Hz), 6.98 (d, 2H, J=9.0Hz), 6.88 (d, 2H, J=9.0Hz), 6.87 (d, 2H, J=9.0Hz), 6.40 (dd, 2H, J=1.5Hz, 17.5Hz), 6.13 (dd, 2H, J=10.5Hz, 17.5Hz), 5.82 (dd, 2H, J=1.5Hz, 10.5Hz), 4.62 (t, 2H, J=7.0Hz), 4.17 (t, 4H, J=6.5Hz), 3.94 (t, 2H, J=6.5Hz), 3.94 (t, 2H, J= 6.5Hz), 2.85 (t, 2H, J=7.0Hz), 2.70-2.80 (m, 1H), 2.54-2.70 (m, 3H), 2.25-2.41 (m, 8H), 1.64-1.85(m,16H)、1.41-1.55(m,8H)。
(embodiment 81) compound 43
[changing 142]
Step 1：Intermediate H2 synthesis
[changing 143]
In possessing three neck reactors of thermometer, by 2.00g (12.11mol) 2- diazanyl benzo thiophenes in nitrogen stream Azoles is dissolved in 40ml DMF.7.89g (24.21mol) cesium carbonate and 2.15g (14.53mmol) is added into the solution 3- bromine butyronitrile, all the elements thing is stirred 15 hours in 25 DEG C.After the completion of reaction, 500ml distillation is added into reaction solution Water, with 100ml ethyl acetate extraction 2 times.After organic layer anhydrous sodium sulfate drying, sodium sulphate is filtered out.By filtrate rotation Turn after evaporator concentration, concentrate is passed through into silica gel column chromatography (THF:Toluene=1:9) purify, thus as white solid with 72% yield obtains 2.03g intermediate H2.
The structure of object passes through1H-NMR is identified.
1H-NMR(500MHz,DMSO-d6,TMS,δppm)：7.70 (dd, 1H, J=1.0Hz, 8.0Hz), 7.41 (dd, 1H, J=1.0Hz, 8.0Hz), 7.24 (dt, 1H, J=1.0Hz, 7.5Hz), 7.03 (dt, 1H, J=1.0Hz, 7.5Hz), 5.24 (s, 2H), 4.86-4.96 (m, 1H), 2.80-2.96 (m, 2H), 1.27 (d, 3H, J=6.5Hz).
Step 2：The synthesis of compound 43
In possessing three neck reactors of thermometer, by 1.0g (1.06mmol) change in embodiment 1 in nitrogen stream The intermediate B synthesized in the step 2 that compound 1 is synthesized is dissolved in 30ml THF.0.44ml is added into the solution The intermediate H2 synthesized in above-mentioned steps 1 of the 1N hydrochloric acid and 0.74g (3.20mmol) of (0.44mmol), by all the elements thing Stirred 15 hours in 60 DEG C.After the completion of reaction, reaction solution is concentrated with rotary evaporator, concentrate is passed through into silica gel column chromatography Method (chloroform:THF=40:1) purify, thus obtain 1.04g compound 43 with 85% yield as faint yellow solid.
The structure of object passes through1H-NMR is identified.
1H-NMR(500MHz,CDCl3,TMS,δppm)：8.18(s,1H)、7.65-7.76(m,3H)、7.37(dt,1H,J =1.0Hz, 7.5Hz), 7.21 (dt, 1H, J=1.0Hz, 7.5Hz), 7.13-7.16 (m, 2H), 6.98 (d, 2H, J= 9.0Hz), 6.98 (d, 2H, J=9.0Hz), 6.88 (d, 2H, J=9.0Hz), 6.88 (d, 2H, J=9.0Hz), 6.40 (dd, 2H, J=1.5Hz, 17.5Hz), 6.13 (dd, 2H, J=10.5Hz, 17.5Hz), 5.82 (dd, 2H, J=1.5Hz, 10.5Hz), 4.85-4.94 (m, 1H), 4.17 (t, 4H, J=6.5Hz), 3.94 (t, 2H, J=6.5Hz), 3.94 (t, 2H, J=6.5Hz), 3.28-3.46(m,2H)、2.53-2.80(m,4H)、2.23-2.41(m,8H)、1.64-1.84(m,19H)、1.41-1.55(m, 8H)。
(embodiment 82) compound 44
[changing 144]
Step 1：The synthesis of intermediate compound I 2
[changing 145]
In possessing three neck reactors of thermometer, by 2.00g (12.11mol) 2- diazanyl benzo thiophenes in nitrogen stream Azoles is dissolved in 40ml DMF.7.89g (24.21mol) cesium carbonate and 1.73g (14.53mmol) is added into the solution Propargyl bromide, all the elements thing is stirred 15 hours in 25 DEG C.After the completion of reaction, 500ml distillation is added into reaction solution Water, with 100ml ethyl acetate extraction 2 times.After organic layer anhydrous sodium sulfate drying, sodium sulphate is filtered out.By filtrate rotation Turn after evaporator concentration, concentrate is passed through into silica gel column chromatography (THF:Toluene=1:19) purify, thus as pale yellow colored solid Body obtains 0.69g intermediate compound I 2 with 28% yield.
The structure of object passes through1H-NMR is identified.
1H-NMR(500MHz,DMSO-d6,TMS,δppm)：7.73 (dd, 1H, J=1.0Hz, 8.0Hz), 7.44 (dd, 1H, J=1.0Hz, 8.0Hz), 7.26 (dt, 1H, J=1.0Hz, 7.5Hz), 7.06 (dt, 1H, J=1.0Hz, 7.5Hz), 5.31 (s, 2H), 4.52 (d, 2H, J=2.5Hz), 3.35 (t, 1H, J=2.5Hz).
Step 2：The synthesis of compound 44
In possessing three neck reactors of thermometer, by 1.0g (1.06mmol) change in embodiment 1 in nitrogen stream The intermediate B synthesized in the step 2 that compound 1 is synthesized is dissolved in 30ml THF.0.44ml is added into the solution The intermediate compound I 2 synthesized in above-mentioned steps 1 of the 1N hydrochloric acid and 0.64g (3.20mmol) of (0.44mmol), by all the elements thing Stirred 15 hours in 50 DEG C.After the completion of reaction, reaction solution is concentrated with rotary evaporator, concentrate is passed through into silica gel column chromatography Method (chloroform:THF=40:1) purify, thus obtain 1.10g compound 44 with 92% yield as faint yellow solid.
The structure of object passes through1H-NMR is identified.
1H-NMR(500MHz,CDCl3,TMS,δppm)：7.92(s,1H)、7.67-7.78(m,3H)、7.36(dt,1H,J =1.0Hz, 7.5Hz), 7.20 (dt, 1H, J=1.0Hz, 7.5Hz), 7.11-7.17 (m, 2H), 6.99 (d, 2H, J= 9.0Hz), 6.98 (d, 2H, J=9.0Hz), 6.88 (d, 2H, J=9.0Hz), 6.88 (d, 2H, J=9.0Hz), 6.40 (dd, 2H, J=1.5Hz, 17.5Hz), 6.13 (dd, 2H, J=10.5Hz, 17.5Hz), 5.82 (dd, 2H, J=1.5Hz, 10.5Hz), 5.14 (d, 2H, J=2.0Hz), 4.17 (t, 4H, J=6.5Hz), 3.94 (t, 4H, J=6.5Hz), 2.54-2.76 (m, 4H), 2.24-2.42(m,9H)、1.64-1.84(m,16H)、1.41-1.56(m,8H)。
(embodiment 83) compound 45
[changing 146]
Step 1：Intermediate J2 synthesis
[changing 147]
In possessing three neck reactors of thermometer, by 2.00g (12.11mol) 2- diazanyl benzo thiophenes in nitrogen stream Azoles is dissolved in 40ml DMF.7.89g (24.21mol) cesium carbonate and 1.93g (14.53mmol) is added into the solution The bromo- 1- butine of 4-, all the elements thing is stirred 15 hours in 25 DEG C.Then, reaction solution is heated to 60 DEG C and further stirs 3 Hour.After the completion of reaction, 500ml distilled water is added into reaction solution, with 100ml ethyl acetate extraction 2 times.Will be organic After layer anhydrous sodium sulfate drying, sodium sulphate is filtered out.After filtrate is concentrated with rotary evaporator, concentrate is passed through into silicagel column color Spectrometry (THF:Toluene=1:19) purify, thus obtain 0.98g intermediate J2 with 37% yield as faint yellow solid.
The structure of object passes through1H-NMR is identified.
1H-NMR(500MHz,DMSO-d6,TMS,δppm)：7.68 (dd, 1H, J=1.0Hz, 8.0Hz), 7.39 (dd, 1H, J=1.0Hz, 8.0Hz), 7.22 (dt, 1H, J=1.0Hz, 7.5Hz), 7.01 (dt, 1H, J=1.0Hz, 7.5Hz), 5.33- 5.40(m,1H)、5.29(s,2H)、4.91-4.97(m,2H)、4.32-4.37(m,2H)。
Step 2：The synthesis of compound 45
In possessing three neck reactors of thermometer, by 1.0g (1.06mmol) change in embodiment 1 in nitrogen stream The intermediate B synthesized in the step 2 that compound 1 is synthesized is dissolved in 30ml THF.0.44ml is added into the solution The 1N hydrochloric acid of (0.44mmol) and the intermediate J2 synthesized in above-mentioned steps 1：0.7g (3.20mmol), by all the elements thing in 50 DEG C are stirred 15 hours.After the completion of reaction, reaction solution is concentrated with rotary evaporator, concentrate is passed through into silica gel column chromatography (chloroform:THF=40:1) purify, thus obtain 1.08g compound 45 with 89% yield as faint yellow solid.
The structure of object passes through1H-NMR is identified.
1H-NMR(500MHz,CDCl3,TMS,δppm)：7.76(s,1H)、7.66-7.76(m,3H)、7.35(dt,1H,J =1.0Hz, 7.5Hz), 7.18 (dt, 1H, J=1.0Hz, 7.5Hz), 7.09-7.13 (m, 2H), 6.99 (d, 2H, J= 9.0Hz), 6.98 (d, 2H, J=9.0Hz), 6.88 (d, 4H, J=9.0Hz), 6.40 (dd, 2H, J=1.5Hz, 17.5Hz), 6.13 (dd, 2H, J=10.5Hz, 17.5Hz), 5.82 (dd, 2H, J=1.5Hz, 10.5Hz), 5.19-5.27 (m, 1H), 4.93-4.99 (m, 2H), 4.83-4.89 (m, 2H), 4.18 (t, 4H, J=6.5Hz), 3.95 (t, 4H, J=6.5Hz), 2.54- 2.74(m,4H)、2.24-2.40(m,8H)、1.63-1.84(m,16H)、1.41-1.56(m,8H)。
(embodiment 84) compound 46
[changing 148]
Step 1：Intermediate K2 synthesis
[changing 149]
In possessing three neck reactors of thermometer, by 10.0g (72.4mol) 2,5- dihydroxy benzenes first in nitrogen stream Aldehyde is dissolved in 200ml dichloromethane.The solution is cooled to 0 DEG C, 35.06g (0.27mol) diisopropyl second is added Amine, with the Chloromethyl methyl ether that 23.32g (0.29mol) is added dropwise for 10 minutes, after completion of dropwise addition, it is 25 DEG C to make reaction solution, in phase Synthermal lower stirring 15 hours.After the completion of reaction, 1000ml distilled water is added into reaction solution, with 200ml dichloromethane Alkane is extracted 2 times.After organic layer anhydrous sodium sulfate drying, sodium sulphate is filtered out., will be dense after filtrate is concentrated with rotary evaporator Contracting thing passes through silica gel column chromatography (THF:Toluene=1:19) purify, 13.26g is thus obtained with 81% yield as colorless oil Intermediate K2.
The structure of object passes through1H-NMR is identified.
1H-NMR(500MHz,CDCl3,TMS,δppm)：10.46 (s, 1H), 7.49 (d, 1H, J=3.0Hz), 7.23 (dd, 1H, J=3.0Hz, 9.0Hz), 7.17 (d, 1H, J=9.0Hz), 5.25 (s, 2H), 5.15 (s, 2H), 3.52 (s, 3H), 3.47 (s,3H)。
Step 2：Intermediate L2 synthesis
[changing 150]
In possessing three neck reactors of thermometer, in nitrogen stream by 11.04g (48.8mol) in above-mentioned steps 1 The intermediate K2 of synthesis is dissolved in 400ml ethanol.6.40g (58.56mmol) 2- hydrazino pyridines are added into the solution, All the elements thing is stirred 3 hours in 25 DEG C.After the completion of reaction, 400ml distilled water is added into reaction solution, leaching is separated out Crystallization, after being cleaned with distilled water, vacuum drying, 11.16g centre is thus obtained with 72% yield as faint yellow solid Body L2.
The structure of object passes through1H-NMR is identified.
1H-NMR(500MHz,DMSO-d6,TMS,δppm)：10.93(s,1H)、8.34(s,1H)、8.07-8.12(m, 1H), 7.61-7.67 (m, 1H), 7.52 (d, 1H, J=3.0Hz), 7.23 (d, 1H, J=8.5Hz), 7.09 (d, 1H, J= 9.0Hz), 6.96 (dd, 1H, J=3.0Hz, 9.0Hz), 6.73-6.78 (m, 1H), 5.20 (s, 2H), 5.18 (s, 2H), 3.42 (s,3H)、3.40(s,3H)。
Step 3：Intermediate M2 synthesis
[changing 151]
In possessing three neck reactors of thermometer, in nitrogen stream by 10.0g (31.5mol) in step 2 above The intermediate L2 of synthesis is dissolved in 300ml THF.14.0g (34.7mmol) hydrogenation was added into the solution with 30 minutes Sodium (oiliness：50~72%), further stirred 30 minutes in 25 DEG C.Then, 5.9g (34.7mmol) 2- chlorobenzenes and thiophene is added Azoles, reaction solution is heated and stirred 8 hours under reflux conditions.Then, into reaction solution add 2000ml distilled water and 500ml saturated aqueous common salt, with 1000ml ethyl acetate extraction 2 times.After organic layer anhydrous sodium sulfate drying, sulphur is filtered out Sour sodium.After filtrate is concentrated with rotary evaporator, concentrate is passed through into silica gel column chromatography (THF:Toluene=1:19) purify, by This obtains 8.8g intermediate M2 as faint yellow solid with 62% yield.
The structure of object passes through1H-NMR is identified.
1H-NMR(500MHz,CDCl3,TMS,δppm)：8.69-8.75(m,1H)、8.19(s,1H)、7.99(dt,1H,J =2.0Hz, 7.5Hz), 7.71-7.79 (m, 2H), 7.59-7.67 (m, 2H), 7.37-7.43 (m, 1H), 7.28-7.33 (m, 1H)、7.15-7.21(m,2H)、7.01-7.04(m,1H)、5.22(s,2H)、5.03(s,2H)、3.54(s,3H)、3.36(s, 3H)。
Step 4：Intermediate N2 synthesis
[changing 152]
In possessing three neck reactors of thermometer, 8.4g (18.7mol) is closed in above-mentioned steps 3 in nitrogen stream Into intermediate M2 be dissolved in 300ml ethanol, add 17.7g (93.2mmol) p-methyl benzenesulfonic acid monohydrate, by institute There is content to be stirred 15 hours in 25 DEG C.Then, 2000ml distilled water and 500ml saturated common salt are added into reaction solution Water, with 1500ml ethyl acetate extraction 2 times.After organic layer anhydrous sodium sulfate drying, sodium sulphate is filtered out.By filtrate rotation Turn after evaporator concentration, 150ml methanol is added into concentrate.It is clear with methanol by filtering the crystallization of leaching insoluble component After washing, thus vacuum drying obtains 3.1g intermediate N2 as yellow solid with 46% yield.
The structure of object passes through1H-NMR is identified.
1H-NMR(500MHz,DMSO-d6,TMS,δppm)：9.28(s,1H)、9.01(s,1H)、8.74-8.78(m,1H)、 8.17 (dt, 1H, J=2.0Hz, 7.5Hz), 7.92 (dd, 1H, J=1.0Hz, 8.0Hz), 7.86 (s, 1H), 7.72-7.76 (m, 1H), 7.58-7.63 (m, 1H), 7.51 (d, 1H, J=8.0Hz), 7.32 (dt, 1H, J=1.0Hz, 7.5Hz), 7.25-7.28 (m, 1H), 7.21 (dt, 1H, J=1.0Hz, 7.5Hz), 6.70-6.72 (m, 2H).
Step 5：Compound 46
In possessing three neck reactors of thermometer, by 10.4g (24.8mmol) change in embodiment 1 in nitrogen stream The intermediate A synthesized in the step 1 that compound 1 is synthesized is dissolved in 150ml THF.2.9g is added into the solution The mesyl chloride of (25.7mmol), reactor is impregnated in water-bath and makes temperature in reaction solution be 20 DEG C, is added dropwise with 10 minutes 2.7g (26.5mmol) triethylamine.After completion of dropwise addition, water-bath is removed, all the elements thing is stirred 2 hours in 25 DEG C.Connect , add 0.2g (1.7mmol) 4- (dimethylamino) pyridine, 3.0g (8.3mmol) centre synthesized in above-mentioned steps 4 Body N2, further with the triethylamine that 2.5g (24.8mmol) is added dropwise for 10 minutes.After completion of dropwise addition, by all the elements thing in 25 DEG C Stirring 2 hours.After the completion of reaction, 2000ml distilled water and 500ml saturated aqueous common salt are added into reaction solution, is used 1000ml chloroform is extracted 2 times.After organic layer anhydrous sodium sulfate drying, sodium sulphate is filtered out.By filtrate rotary evaporator After concentration, pass through silica gel column chromatography (chloroform:THF=25:1) purify, thus obtained as faint yellow solid with 19% yield To 1.8g compound 46.
The structure of object passes through1H-NMR is identified.
1H-NMR(500MHz,CDCl3,TMS,δppm)：8.70-8.74 (m, 1H), 8.02 (dt, 1H, J=2.0Hz, 7.5Hz), 7.87 (s, 1H), 7.83 (d, 1H, J=2.5Hz), 7.74-7.78 (m, 1H), 7.62-7.67 (m, 2H), 7.42- 7.46 (m, 1H), 7.34 (dt, 1H, J=1.0Hz, 7.5Hz), 7.22 (dt, 1H, J=1.0Hz, 7.5Hz), 7.07-7.15 (m, 2H), 6.96-7.01 (m, 4H), 6.90 (d, 2H, J=9.0Hz), 6.88 (d, 2H, J=9.0Hz), 6.41 (dd, 1H, J= 1.5Hz, 17.5Hz), 6.41 (dd, 1H, J=1.5Hz, 17.5Hz), 6.13 (dd, 1H, J=10.5Hz, 17.5Hz), 6.13 (dd, 1H, J=10.5Hz, 17.5Hz), 5.82 (dd, 1H, J=1.5Hz, 10.5Hz), 5.82 (dd, 1H, J=1.5Hz, 10.5Hz), 4.18 (t, 2H, J=6.5Hz), 4.18 (t, 2H, J=6.5Hz), 3.95 (t, 2H, J=6.5Hz), 3.95 (t, 2H, J=6.5Hz), 2.56-2.71 (m, 2H), 2.25-2.50 (m, 6H), 2.12-2.21 (m, 2H), 1.93-2.01 (m, 2H), 1.65-1.85(m,12H)、1.31-1.61(m,12H)。
(embodiment 85) compound 47
[changing 153]
Step 1：Intermediate O2 synthesis
[changing 154]
In nitrogen stream into the three neck reactors for possess thermometer add 1.68g (10.61mol) o-tolyl hydrazine and 50ml ethanol.1.34g (13.26mol) triethylamine is added into the solution, all the elements thing is stirred 10 points in 25 DEG C Clock.In the step 1 that addition 2.00g (8.84mol) compound 46 in above-described embodiment 84 is synthesized into obtained mixture The intermediate K2 of synthesis, all the elements thing is stirred 1 hour in 25 DEG C.After the completion of reaction, add 300ml's into reaction solution The saturated aqueous common salt of distilled water and 50ml, with 100ml ethyl acetate extraction 2 times.After organic layer anhydrous sodium sulfate drying, Filter out sodium sulphate.After filtrate is concentrated with rotary evaporator, concentrate is passed through into silica gel column chromatography (THF:Toluene=1:25) Purifying, thus obtains 2.81g intermediate O2 as faint yellow solid with 96% yield.
The structure of object passes through1H-NMR is identified.
1H-NMR(500MHz,CDCl3,TMS,δppm)：8.16 (s, 1H), 7.69 (d, 1H, J=3.0Hz), 7.57 (dd, 1H, J=1.0Hz, 8.0Hz), 7.14-7.26 (m, 2H), 7.03-7.11 (m, 2H), 6.95 (dd, 1H, J=3.0Hz, 9.0Hz), 6.81 (dt, 1H, J=1.0Hz, 7.5Hz), 5.18 (s, 2H), 5.18 (s, 2H), 3.51 (s, 3H), 3.50 (s, 3H)、2.24(s,3H)。
Step 2：Intermediate P2 synthesis
[changing 155]
In possessing three neck reactors of thermometer, by the intermediate O2 synthesized in above-mentioned steps 1 in nitrogen stream： 2.78g (8.42mol) is dissolved in 50ml THF.0.54g (13.46mmol) was added into the solution with 15 minutes in 25 DEG C Sodium hydride (oiliness：50~72%), stir 30 minutes.Then, 2.14g (12.62mmol) 2- chloro benzothiazoles are added, will Reaction solution is stirred 2 hours under heated reflux condition.After the completion of reaction, into reaction solution add 400ml distilled water and 50ml saturated aqueous common salt, with 150ml ethyl acetate extraction 2 times.After organic layer anhydrous sodium sulfate drying, sulfuric acid is filtered out Sodium.After filtrate is concentrated with rotary evaporator, concentrate is passed through into silica gel column chromatography (THF:Toluene=3:100) purify, by This obtains 2.66g intermediate P2 as faint yellow solid with 68% yield.
The structure of object passes through1H-NMR is identified.
1H-NMR(500MHz,CDCl3,TMS,δppm)：7.76 (d, 1H, J=3.0Hz), 7.72 (dd, 1H, J=1.0Hz, 8.0Hz), 7.60 (dd, 1H, J=1.0Hz, 8.0Hz), 7.54 (s, 1H), 7.41-7.48 (m, 3H), 7.25-7.34 (m, 2H), 7.11-7.21(m,1H)、6.95-7.03(m,2H)、5.22(s,2H)、4.98(s,2H)、3.55(s,3H)、3.26(s,3H)、 2.16(s,3H)。
Step 3：Intermediate Q2 synthesis
[changing 156]
In possessing three neck reactors of thermometer, in nitrogen stream by 2.65g (5.72mol) in step 2 above The intermediate P2 of synthesis is dissolved in 80ml ethanol.5.44g (28.58mmol) p-methyl benzenesulfonic acid one is added into the solution Hydrate is simultaneously stirred 15 hours.After the completion of reaction, after reaction solution is concentrated with rotary evaporator, 40ml methanol is added.It is logical The crystallization of leaching insoluble component is filtered, after being cleaned with methanol, thus vacuum drying is obtained as yellow solid with 88% yield To 1.88g intermediate Q2.
The structure of object passes through1H-NMR is identified.
1H-NMR(500MHz,DMSO-d6,TMS,δppm)：7.90 (dd, 1H, J=1.0Hz, 8.0Hz), 7.46-7.58 (m, 5H), 7.39-7.42 (m, 1H), 7.25-7.33 (m, 2H), 7.18 (dt, 1H, J=1.0Hz, 7.5Hz), 7.10-7.15 (m,2H)、6.69(s,1H)、6.69(s,1H)、2.29(s,3H)。
Step 4：Compound 47
In possessing three neck reactors of thermometer, by 5.36g (12.78mmol) in embodiment 1 in nitrogen stream The intermediate A synthesized in the step 1 that compound 1 is synthesized is dissolved in 60ml THF.1.52g is added into the solution The mesyl chloride of (13.22mmol), reactor is impregnated in water-bath and makes temperature in reaction solution be 20 DEG C, is added dropwise with 5 minutes 1.38g (13.7mmol) triethylamine.Then, water-bath is removed, all the elements thing is stirred 2 hours in 25 DEG C.And then, add 0.1g (0.82mmol) 4- (dimethylamino) pyridine, 1.60g (4.26mmol) intermediate synthesized in above-mentioned steps 3 Q2, further with the triethylamine that 1.30g (12.78mmol) is added dropwise for 5 minutes.After completion of dropwise addition, by all the elements thing in 25 DEG C Stirring 2 hours.After the completion of reaction, 400ml distilled water and 100ml saturated aqueous common salt are added into reaction solution, 200ml is used Chloroform extract 2 times.After organic layer anhydrous sodium sulfate drying, sodium sulphate is filtered out.After filtrate is concentrated with rotary evaporator, Concentrate is passed through into silica gel column chromatography (chloroform:THF=40:1) purify, thus obtained as faint yellow solid with 21% yield To 1.04g compound 47.
The structure of object passes through1H-NMR is identified.
1H-NMR(500MHz,CDCl3,TMS,δppm)：7.84 (d, 1H, J=3.0Hz), 7.73 (dt, 1H, J=1.0Hz, 8.0Hz), 7.61 (d, 1H, J=8.0Hz), 7.44-7.52 (m, 3H), 7.27-7.34 (m, 2H), 7.15-7.20 (m, 2H), 7.10 (dd, 1H, J=3.0Hz, 9.0Hz), 7.05 (d, 1H, J=9.0Hz), 7.01 (d, 2H, J=9.0Hz), 6.99 (d, 2H, J=9.0Hz), 6.90 (d, 2H, J=9.0Hz), 6.89 (d, 2H, J=9.0Hz), 6.41 (dd, 1H, J=1.5Hz, 17.5Hz), 6.41 (dd, 1H, J=1.5Hz, 17.5Hz), 6.13 (dd, 1H, J=10.5Hz, 17.5Hz), 6.13 (dd, 1H, J =10.5Hz, 17.5Hz), 5.82 (dd, 1H, J=1.5Hz, 10.5Hz), 5.82 (dd, 1H, J=1.5Hz, 10.5Hz), 4.18 (t, 2H, J=6.5Hz), 4.18 (t, 2H, J=6.5Hz), 3.96 (t, 2H, J=6.5Hz), 3.95 (t, 2H, J=6.5Hz), 2.56-2.72(m,2H)、2.42-2.51(m,1H)、2.28-2.40(m,5H)、2.14-2.22(m,2H)、2.14(s,3H)、 1.65-1.91(m,14H)、1.41-1.57(m,10H)、1.19-1.31(m,2H)。
<The measure 3 of phase transition temperature>
10mg compound obtained above 34~47 is weighed respectively, directly with solid state, is sandwiched in 2 and was implemented grinding In the glass substrate with alignment film of polyimide of processing.The substrate is placed on hot plate, 250 DEG C are warming up to from 40 DEG C Afterwards, 40 DEG C are cooled to again.With the change of institutional framework during polarized light microscope observing heating, cooling.
The phase transition temperature of measure is illustrated in following table 5.
[table 6]
Table 5
(embodiment 86~88)
By the respectively 1.0g compound 34~36 obtained in embodiment 72~74,30mg Photoepolymerizationinitiater initiater A, 1% cyclopentanone solution of 100mg surfactant A is dissolved in 2.3g cyclopentanone.The solution is used with 0.45 μm The disposable filter filtering of micropore diameter, obtains polymerizable composition, polymerizable composition 39~41.
(embodiment 89)
The 1.0g compound 37 obtained in embodiment 75,30mg Photoepolymerizationinitiater initiater A, 100mg surface are lived Property agent A 1% cyclopentanone solution is dissolved in 3.0g chloroform.By disposable mistake of the solution with 0.45 μm of micropore diameter Filter is filtered, and obtains polymerizable composition, polymerizable composition 42.
(embodiment 90~93)
By the respectively 1.0g compound 38~41 obtained in embodiment 76~79,30mg Photoepolymerizationinitiater initiater A, 1% cyclopentanone solution of 100mg surfactant A is dissolved in 2.3g cyclopentanone.The solution is used with 0.45 μm The disposable filter filtering of micropore diameter, obtains polymerizable composition, polymerizable composition 43~46.
(embodiment 94)
The 1.0g compound 42 obtained in embodiment 80,30mg Photoepolymerizationinitiater initiater A, 100mg surface are lived Property agent A 1% cyclopentanone solution is dissolved in 3.0g chloroform.By disposable mistake of the solution with 0.45 μm of micropore diameter Filter is filtered, and obtains polymerizable composition, polymerizable composition 47.
(embodiment 95~97)
By the respectively 1.0g compound 43~45 obtained in embodiment 81~83,30mg Photoepolymerizationinitiater initiater A, 1% cyclopentanone solution of 100mg surfactant A is dissolved in 2.3g cyclopentanone.The solution is used with 0.45 μm The disposable filter filtering of micropore diameter, obtains polymerizable composition, polymerizable composition 48~50.
(embodiment 98)
The 1.0g compound 46 obtained in embodiment 84,30mg Photoepolymerizationinitiater initiater A, 100mg surface are lived Property agent A 1% cyclopentanone solution is dissolved in 2.3g chloroform.By disposable mistake of the solution with 0.45 μm of micropore diameter Filter is filtered, and obtains polymerizable composition, polymerizable composition 51.
(embodiment 99)
The 1.0g compound 47 obtained in embodiment 85,30mg Photoepolymerizationinitiater initiater A, 100mg surface are lived Property agent A 1% cyclopentanone solution is dissolved in 2.3g cyclopentanone.The solution is used with the disposable of 0.45 μm of micropore diameter Filter is filtered, and obtains polymerizable composition, polymerizable composition 52.
<The measure of phase difference and the evaluation III of wavelength dispersion>
(i) formation of the liquid crystal layer of polymerizable composition, polymerizable composition is used
In being provided with the transparent glass substrate of alignment film of polyimide for ground processing, it is coated with respectively using #4 bars Polymerizable composition, polymerizable composition 39~52.After film is dried 1 minute at the temperature shown in following table 6, taken at the temperature shown in table 6 To processing 1 minute, liquid crystal layer is formed.Then, 2000mJ/cm is irradiated at the temperature shown in table 6 from the coating surface side of liquid crystal layer2 Ultraviolet polymerize, wavelength dispersion test sample is made.
(ii) evaluation of the measure of phase difference and wavelength dispersion
For obtained sample, pass through the measure of method progress phase difference same as described above, the evaluation of wavelength dispersion.
By the film thickness (μm) of liquid crystal liquid crystal property polymeric membrane obtained from polymerization, the phase difference (Re) of 548.5nm wavelength, α, β Value collect and be illustrated in following table 6.
As shown in Table 6, the macromolecule of the embodiment 86~99 obtained using compound 34~47 involved in the present invention is Optically anisotropic body.In addition, the α of obtained optically anisotropic body, which is less than 1, β, is more than 1 or about 1, wideband is presented in display Preferable wavelength dispersibility with property.
The synthesis of (embodiment 100) compound 48
[changing 157]
Step 1：Intermediate R2 synthesis
[changing 158]
In the four neck reactors for possessing thermometer, by 2.00g (12.1mmol) 2- diazanyl benzo thiophenes in nitrogen stream Azoles is dissolved in 30ml DMF.7.88g (24.2mmol) cesium carbonate, 1.93g (14.5mmol) 1- is added into the solution Bromo- 2- butine, all the elements thing is stirred 20 hours in 25 DEG C.After the completion of reaction, reaction solution is put into 200ml water In, with 300ml ethyl acetate extraction.After ethyl acetate layer anhydrous sodium sulfate drying, sodium sulphate is filtered out.Use rotary evaporation Ethyl acetate is distilled off from filtrate decompression in device, obtains brown solid.By the brown solid by silica gel column chromatography (just oneself Alkane:Ethyl acetate=85:15) purify, 1.25g intermediate R2 (yields are obtained as white solid：47.5%).
The structure of object passes through1H-NMR is identified.
1H-NMR(500MHz,CDCl3,TMS,δppm)：7.63 (dd, 1H, J=1.3Hz, 7.8Hz), 7.58 (dd, 1H, J =1.3Hz, 7.8Hz), 7.29 (ddd, 1H, J=1.3Hz, 7.8Hz, 7.8Hz), 7.10 (ddd, 1H, J=1.3Hz, 7.8Hz, 7.8Hz), 4.56 (q, 2H, J=2.5Hz), 4.36 (s, 2H), 1.84 (t, 3H, J=2.5Hz).
Step 2：The synthesis of compound 48
In the three neck reactors for possessing thermometer, add in nitrogen stream 1.50g (1.60mmol) in embodiment 1 Compound 1 synthesize step 2 in synthesize intermediate B, 387mg (1.78mmol) intermediate synthesized in above-mentioned steps 1 R2,41.4mg (0.165mmol) (±) -10- camphorsulfonic acids, 16ml THF and 4ml ethanol, are made uniform solution.So Afterwards, all the elements thing is stirred 5 hours in 40 DEG C.After the completion of reaction, reaction solution is put into 100ml water, uses 200ml Chloroform extraction.After organic layer anhydrous sodium sulfate drying, sodium sulphate is filtered out., will after filtrate is concentrated with rotary evaporator Concentrate passes through silica gel column chromatography (toluene:Ethyl acetate=9:1) purify, 1.54g chemical combination is obtained as faint yellow solid (the yield of thing 48：84.9%).
The structure of object passes through1H-NMR is identified.
1H-NMR(500MHz,CDCl3,TMS,δppm)：7.90 (s, 1H), 7.78 (d, 1H, J=1.3Hz), 7.67-7.73 (m, 2H), 7.35 (ddd, 1H, J=1.3Hz, 7.5Hz, 7.5Hz), 7.18 (ddd, 1H, J=1.3Hz, 7.5Hz, 7.5Hz), 7.09-7.15 (m, 2H), 6.95-7.01 (m, 4H), 6.85-6.91 (m, 4H), 6.40 (dd, 2H, J=1.5Hz, 17.0Hz), 6.13 (dd, 2H, J=10.5Hz, 17.0Hz), 5.82 (dd, 2H, J=1.5Hz, 10.5Hz), 5.06 (d, 2H, J=2.0Hz), 4.18 (t, 4H, J=6.0Hz), 3.95 (t, 4H, J=6.0Hz), 2.55-2.76 (m, 4H), 2.26-2.43 (m, 8H), 1.64- 1.83(m,19H)、1.41-1.55(m,8H)。
The synthesis of (embodiment 101) compound 49
[changing 159]
Step 1：Intermediate S2 synthesis
[changing 160]
In the three neck reactors for possessing thermometer, by 2.00g (12.1mmol) 2- diazanyl benzo thiophenes in nitrogen stream Azoles is dissolved in 30ml DMF.7.88g (24.2mol) cesium carbonate is added into the solution and 0 DEG C is cooled to, with 5 minutes drops Plus 2.50g (14.5mmol) the chloro- 3- decine of 10-.After completion of dropwise addition, all the elements thing is stirred 5 hours in 25 DEG C.Anti- After should terminating, reaction solution is put into 200ml water, with 300ml ethyl acetate extraction.Ethyl acetate layer is used into anhydrous sulphur After sour sodium is dried, sodium sulphate is filtered out.Ethyl acetate is distilled off from filtrate decompression with rotary evaporator, brown solid is obtained.Will The brown solid passes through silica gel column chromatography (n-hexane:Ethyl acetate=85:15) purify, 1.51g is obtained as white solid Intermediate S2 (yields：41.4%).
The structure of object passes through1H-NMR is identified.
1H-NMR(500MHz,CDCl3,TMS,δppm)：7.60 (dd, 1H, J=1.5Hz, 7.5Hz), 7.53 (dd, 1H, J =1.5Hz, 7.5Hz), 7.28 (ddd, 1H, J=1.5Hz, 7.5Hz, 7.5Hz), 7.06 (ddd, 1H, J=1.5Hz, 7.5Hz, 7.5Hz), 4.23 (s, 2H), 3.75 (t, 2H, J=7.5Hz), 2.09-2.21 (m, 4H), 1.75 (tt, 2H, J=7.5Hz, 7.5Hz), 1.35-1.54 (m, 6H), 1.11 (t, 3H, J=7.5Hz).
Step 2：The synthesis of compound 49
Add into the three neck reactors for possess thermometer in nitrogen stream 1.50g (1.60mmol) in embodiment 1 Compound 1 synthesize step 2 in synthesize intermediate B, 534mg (1.78mmol) intermediate synthesized in above-mentioned steps 1 S2,41.4mg (0.178mmol) (±) -10- camphorsulfonic acids, 16ml THF and 4ml ethanol, are made uniform solution.So Afterwards, all the elements thing is stirred 3 hours in 40 DEG C.After the completion of reaction, reaction solution is put into 100ml water, uses 200ml Chloroform extraction.After organic layer anhydrous sodium sulfate drying, sodium sulphate is filtered out., will after filtrate is concentrated with rotary evaporator Concentrate passes through silica gel column chromatography (toluene:Ethyl acetate=92:8) purify, 1.62g chemical combination is obtained as faint yellow solid (the yield of thing 49：83.8%).
The structure of object passes through1H-NMR is identified.
1H-NMR(500MHz,CDCl3,TMS,δppm)：7.75 (d, 1H, J=1.5Hz), 7.65-7.71 (m, 3H), 7.34 (ddd, 1H, J=1.5Hz, 7.8Hz, 7.8Hz), 7.17 (ddd, 1H, J=1.5Hz, 7.8Hz, 7.8Hz), 7.08-7.14 (m, 2H), 6.95-7.01 (m, 4H), 6.85-6.91 (m, 4H), 6.40 (dd, 2H, J=1.5Hz, 17.5Hz), 6.13 (dd, 2H, J =10.5Hz, 17.5Hz), 5.82 (dd, 2H, J=1.5Hz, 10.5Hz), 4.31 (t, 2H, J=7.5Hz), 4.18 (t, 4H, J =6.5Hz), 3.94 (t, 4H, J=6.5Hz), 2.54-2.74 (m, 4H), 2.25-2.40 (m, 8H), 2.09-2.19 (m, 4H), 1.63-1.85 (m, 18H), 1.38-1.55 (m, 14H), 1.09 (t, 3H, J=7.5Hz).
The synthesis of (embodiment 102) compound 50
[changing 161]
Step 1：Intermediate T2 synthesis
[changing 162]
Intermediate T2
In the three neck reactors for possessing thermometer, by 3.00g (18.2mmol) 2- diazanyl benzo thiophenes in nitrogen stream Azoles is dissolved in 40ml DMF.11.9g (36.4mol) cesium carbonate is added into the solution and 0 DEG C is cooled to, with 5 minutes drops Plus 4.15g (21.8mmol) chloromethyl phenyl sulfone.After completion of dropwise addition, all the elements thing is stirred 6 hours in 25 DEG C.Anti- After should terminating, 300ml water is added into reaction solution, with 200ml ethyl acetate extraction 2 times.By organic layer anhydrous slufuric acid After sodium is dried, sodium sulphate is filtered out.After filtrate is concentrated with rotary evaporator, concentrate is passed through into silica gel column chromatography (n-hexane: Ethyl acetate=75:25) purify, 1.81g intermediate T2 (yields are thus obtained as white solid：31.2%).
The structure of object passes through1H-NMR is identified.
1H-NMR(500MHz,CDCl3,TMS,δppm)：7.85-7.90 (m, 2H), 7.55 (dd, 1H, J=1.5Hz, 7.3Hz), 7.32-7.43 (m, 3H), 7.13-7.21 (m, 2H), 7.05 (ddd, 1H, J=1.5Hz, 7.3Hz, 7.3Hz), 5.25 (s,2H)、4.99(s,2H)。
Step 2：The synthesis of compound 50
Add into the three neck reactors for possess thermometer in nitrogen stream 1.50g (1.60mmol) in embodiment 1 Compound 1 synthesize step 2 in synthesize intermediate B, 567mg (1.78mmol) intermediate synthesized in above-mentioned steps 1 T2,41.4mg (0.178mmol) (±) -10- camphorsulfonic acids, 16ml THF and 4ml ethanol, are made uniform solution.So Afterwards, all the elements thing is stirred 5 hours in 40 DEG C.After the completion of reaction, reaction solution is put into 100ml water, uses 200ml Chloroform extraction.After organic layer anhydrous sodium sulfate drying, sodium sulphate is filtered out., will after filtrate is concentrated with rotary evaporator Concentrate passes through silica gel column chromatography (toluene:Ethyl acetate=9:1) purify, 1.53g chemical combination is obtained as faint yellow solid (the yield of thing 50：77.3%).
The structure of object passes through1H-NMR is identified.
1H-NMR(500MHz,CDCl3,TMS,δppm)：8.50 (s, 1H), 7.87-7.95 (m, 2H), 7.72 (d, 1H, J= 1.3Hz), 7.61 (d, 1H, J=7.5Hz), 7.33-7.45 (m, 4H), 7.27 (ddd, 1H, J=1.3Hz, 7.5Hz, 7.5Hz), 7.16-7.20 (m, 2H), 7.15 (ddd, 1H, J=1.3Hz, 7.5Hz, 7.5Hz), 6.94-7.01 (m, 4H), 6.84-6.91 (m, 4H), 6.40 (dd, 2H, J=1.5Hz, 17.5Hz), 6.12 (dd, 2H, J=10.0Hz, 17.5Hz), 5.82 (dd, 2H, J =1.5Hz, 10.0Hz), 5.61 (s, 2H), 4.17 (t, 4H, J=6.5Hz), 3.94 (t, 4H, J=6.5Hz), 2.73-2.86 (m,1H)、2.54-2.71(m,3H)、2.40-2.49(m,2H)、2.29-2.39(m,6H)、1.62-1.84(m,16H)、1.40- 1.54(m,8H)。
The synthesis of (embodiment 103) compound 51
[changing 163]
Step 1：Intermediate U2 synthesis
[changing 164]
In the three neck reactors for possessing thermometer, by 3.00g (18.2mmol) 2- diazanyl benzo thiophenes in nitrogen stream Azoles is dissolved in 40ml DMF.11.9g (36.4mol) cesium carbonate is added into the solution and 0 DEG C is cooled to, with 5 minutes drops Plus 4.34g (21.8mmol) phenacyl bromide.After completion of dropwise addition, all the elements thing is stirred 5 hours in 25 DEG C.In reaction After end, 250ml water is added into reaction solution, with 100ml ethyl acetate extraction 2 times.By organic layer anhydrous sodium sulfate After drying, sodium sulphate is filtered out.After filtrate is concentrated with rotary evaporator, concentrate is passed through into silica gel column chromatography (n-hexane:Vinegar Acetoacetic ester=75:25) purify, 1.79g intermediate U2 (yields are thus obtained as white solid：34.7%).
The structure of object passes through1H-NMR is identified.
1H-NMR(500MHz,CDCl3,TMS,δppm)：7.99 (dd, 2H, J=1.3Hz, 7.5Hz), 7.59-7.66 (m, 2H), 7.44-7.53 (m, 3H), 7.25 (ddd, 1H, J=1.3Hz, 7.5Hz, 7.5Hz), 7.08 (ddd, 1H, J=1.3Hz, 7.5Hz,7.5Hz)、5.31(s,2H)、4.65(s,2H)。
Step 2：The synthesis of compound 51
Add into the three neck reactors for possess thermometer in nitrogen stream 1.50g (1.60mmol) in embodiment 1 Compound 1 synthesize step 2 in synthesize intermediate B, 504mg (1.78mmol) intermediate synthesized in above-mentioned steps 1 U2,41.4mg (0.178mmol) (±) -10- camphorsulfonic acids, 16ml THF and 4ml ethanol, are made uniform solution.So Afterwards, all the elements thing is stirred 5 hours in 40 DEG C.After the completion of reaction, reaction solution is put into 100ml water, uses 200ml Chloroform extraction.After organic layer anhydrous sodium sulfate drying, sodium sulphate is filtered out., will after filtrate is concentrated with rotary evaporator Concentrate passes through silica gel column chromatography (toluene:Ethyl acetate=85:15) purify, 1.59g change is obtained as faint yellow solid (the yield of compound 51：82.9%).
The structure of object passes through1H-NMR is identified.
1H-NMR(500MHz,CDCl3,TMS,δppm)：8.12 (dd, 2H, J=1.0Hz, 7.5Hz), 7.76 (d, 1H, J= 2.5Hz), 7.72 (dd, 1H, J=1.0Hz, 7.5Hz), 7.60-7.69 (m, 2H), 7.53-7.59 (m, 2H), 7.42 (s, 1H), 7.34 (ddd, 1H, J=1.0Hz, 7.5Hz, 7.5Hz), 7.19 (ddd, 1H, J=1.0Hz, 7.5Hz, 7.5Hz), 7.06-7.12 (m, 2H), 6.95-7.01 (m, 4H), 6.86-6.93 (m, 4H), 6.40 (dd, 2H, J=1.5Hz, 17.5Hz), 6.13 (dd, 2H, J=10.5Hz, 17.5Hz), 5.83 (dd, 2H, J=1.5Hz, 10.5Hz), 5.82 (s, 2H), 4.18 (t, 4H, J= 6.5Hz), 3.95 (t, 4H, J=6.5Hz), 2.55-2.72 (m, 2H), 2.20-2.42 (m, 6H), 1.87-2.09 (m, 4H), 1.64-1.85(m,12H)、1.32-1.56(m,12H)。
The synthesis of (embodiment 104) compound 52
[changing 165]
Step 1：Intermediate V2 synthesis
[changing 166]
In the three neck reactors for possessing thermometer, by 3.00g (18.2mmol) 2- diazanyl benzo thiophenes in nitrogen stream Azoles is dissolved in 30ml DMF.11.9g (36.4mol) cesium carbonate is added into the solution and 0 DEG C is cooled to, with 5 minutes drops Plus 4.03g (21.8mmol) 2- phenylethyl bromines.After completion of dropwise addition, all the elements thing is stirred 25 hours in 25 DEG C. After reaction terminates, 250ml water is added into reaction solution, with 100ml ethyl acetate extraction 2 times.By the anhydrous sulphur of organic layer After sour sodium is dried, sodium sulphate is filtered out.After filtrate is concentrated with rotary evaporator, by concentrate by silica gel column chromatography (just oneself Alkane:Ethyl acetate=78:22) purify, 2.10g intermediate V2 (yields are thus obtained as white solid：42.9%).
The structure of object passes through1H-NMR is identified.
1H-NMR(500MHz,CDCl3,TMS,δppm)：7.60 (dd, 1H, J=1.3Hz, 7.8Hz), 7.56 (dd, 1H, J =1.3Hz, 7.8Hz), 7.20-7.36 (m, 6H), 7.07 (ddd, 1H, J=1.3Hz, 7.8Hz, 7.8Hz), 4.05 (s, 2H), 4.01 (t, 2H, J=7.3Hz), 3.07 (t, 2H, J=7.3Hz).
Step 2：The synthesis of compound 52
Add into the three neck reactors for possess thermometer in nitrogen stream 1.50g (1.60mmol) in embodiment 1 Compound 1 synthesize step 2 in synthesize intermediate B, 477mg (1.78mmol) intermediate synthesized in above-mentioned steps 1 V2,41.4mg (0.178mmol) (±) -10- camphorsulfonic acids, 16ml THF and 4ml ethanol, are made uniform solution.So Afterwards, all the elements thing is stirred 5 hours in 40 DEG C.After the completion of reaction, reaction solution is put into 100ml water, uses 200ml Chloroform extraction.After organic layer anhydrous sodium sulfate drying, sodium sulphate is filtered out., will after filtrate is concentrated with rotary evaporator Concentrate passes through silica gel column chromatography (toluene:Ethyl acetate=92:8) purify, 1.56g chemical combination is obtained as faint yellow solid (the yield of thing 52：82.3%).
The structure of object passes through1H-NMR is identified.
1H-NMR(500MHz,CDCl3,TMS,δppm)：7.76 (d, 1H, J=1.5Hz), 7.68-7.73 (m, 3H), 7.29-7.39 (m, 5H), 7.22-7.26 (m, 1H), 7.19 (ddd, 1H, J=1.5Hz, 8.5Hz, 8.5Hz), 7.08-7.14 (m, 2H), 6.95-7.02 (m, 4H), 6.86-6.92 (m, 4H), 6.40 (dd, 2H, J=1.5Hz, 17.0Hz), 6.13 (dd, 2H, J=10.5Hz, 17.0Hz), 5.82 (dd, 2H, J=1.5Hz, 10.5Hz), 4.54 (t, 2H, J=5.5Hz), 4.18 (t, 4H, J=6.5Hz), 3.95 (t, 4H, J=6.5Hz), 3.06 (t, 2H, J=5.5Hz), 2.56-2.71 (m, 3H), 2.42- 2.53(m,1H)、2.13-2.40(m,8H)、1.59-1.84(m,16H)、1.41-1.56(m,8H)。
<The measure 4 of phase transition temperature>
10mg compound obtained above 48~52 is weighed respectively, directly with solid state, is sandwiched in 2 and was implemented grinding In the glass substrate with alignment film of polyimide of processing.The substrate is placed on hot plate, 250 DEG C are warming up to from 40 DEG C Afterwards, 40 DEG C are cooled to again.With the change of institutional framework during polarized light microscope observing heating, cooling.
The phase transition temperature of measure is illustrated in following table 7.
[table 8]
Table 7
(embodiment 105~109)
By the respectively 1.0g compound 48~52 obtained in embodiment 100~104,30mg Photoepolymerizationinitiater initiater 1% cyclopentanone solution of A, 100mg surfactant A is dissolved in 2.3g cyclopentanone.The solution, which is used, has 0.45 μm Micropore diameter disposable filter filtering, obtain polymerizable composition, polymerizable composition 53~57.
<The measure of phase difference and the evaluation IV of wavelength dispersion>
(i) formation of the liquid crystal layer of polymerizable composition, polymerizable composition is used
In being provided with the transparent glass substrate of alignment film of polyimide for ground processing, it is coated with respectively using #4 bars Polymerizable composition, polymerizable composition 53~57.After film is dried 1 minute at the temperature shown in following table 8, taken at the temperature shown in table 8 To processing 1 minute, liquid crystal layer is formed.Then, 2000mJ/cm is irradiated at the temperature shown in table 8 from the coating surface side of liquid crystal layer2 Ultraviolet polymerize, wavelength dispersion test sample is made.
(ii) measure of phase difference, the evaluation of wavelength dispersion
For obtained sample, pass through the measure of method progress phase difference same as described above, the evaluation of wavelength dispersion.
By the film thickness (μm) of liquid crystal liquid crystal property polymeric membrane obtained from polymerization, the phase difference (Re) of 548.5nm wavelength, α, β Value collect and be illustrated in following table 8.
As shown in Table 8, the macromolecule of the embodiment 105~109 obtained using compound 48~52 involved in the present invention For optically anisotropic body.In addition, the α of obtained optically anisotropic body, which is less than 1, β, is more than 1, broadband is presented in display Preferable wavelength dispersibility.
(embodiment 110)
By 19.3 parts of the compound 4 obtained in example 4,0.6 part of Photoepolymerizationinitiater initiater B (BASF Japan Ltd. make, Irgacure 379), 5.8 parts of surfactant B (AGC Seimi Chemical Co., Ltd.s system, Surflon S-420 1% cyclopentanone solution) is dissolved in 74.2 parts of cyclopentanone, with the disposable filter of the micropore diameter with 0.6 μm Filtering, obtains polymerizable composition, polymerizable composition 58.
(embodiment 111)
In embodiment 110, instead of the compound 4 obtained in example 4, the chemical combination obtained in embodiment 26 is used Thing 13, in addition, obtains polymerizable composition, polymerizable composition 59 identically with embodiment 110.
(embodiment 112)
In embodiment 110, instead of the compound 4 obtained in example 4, the chemical combination obtained in embodiment 35 is used Thing 22, in addition, obtains polymerizable composition, polymerizable composition 60 identically with embodiment 110.
(comparative example 3)
In embodiment 110, instead of the compound 4 obtained in example 4, the chemical combination obtained in synthesis example 1 is used Thing A, in addition, obtains polymerizable composition, polymerizable composition 61 identically with embodiment 110.
<The measure of phase difference and the evaluation of reflecting brightness>
Obtained polymerizable composition, polymerizable composition 58~61 is polymerize by following method and macromolecule is obtained.For obtained high score Son, carries out the measure of phase difference and the evaluation of reflecting brightness respectively.
(preparation of polarizer)
By the way that a face of support (Zeon Corporation systems, Zeonor Film, trade name " ZF16 ") is ground Grind and carry out orientation process.Being respectively coated polymerizable composition, polymerizable composition 58~61 obtained above with spin coater on the face makes to do Dry film thickness is respectively 2.5 μm, 1.9 μm, 1.9 μm and 1.4 μm.By using baking oven in 130 DEG C (to polymerizable composition, polymerizable composition 60 be 105 DEG C) heat 2 minutes, polymerizable composition, polymerizable composition layer is dried.Thus, the drying for obtaining being formed by support and on support it is poly- The lamilate that conjunction property composition layer is constituted.
Then, it polymerize polymerizable compound above-mentioned lamilate irradiation ultraviolet radiation using metal halide lamp.Ultraviolet Exposure be, in 16mW/cm2Illumination under make light exposure be 100mJ/cm2.Thus, obtain by support and be arranged on support The polarizer that optically anisotropic body layer on body is constituted.The film thickness of obtained optically anisotropic body layer is respectively 2.5 μ M, 1.9 μm, 1.9 μm and 1.4 μm.
For obtained polarizer, phase difference analysis apparatus (AXOMETRICS company systems, trade name are used： AxoScan), it is the phase difference Re (550) under λ=550nm to determine wavelength.Its result is illustrated in table 9.
(preparation of circular polarizer)
By by obtained polarizer and linear polarizer (SANRITZ company systems, trade name：HLC2-5618) use up Learn and use transparent adhesive material (Dong electrician society system, trade name：LUCIACS) fit, prepare circular polarizer.Now, make linear inclined The direction of principal axis that absorbs of tabula rasa is 45 ° with the relative angle of the slow-axis direction (direction parallel with grinding direction) of polarizer.
(calculating of the reflecting brightness of circular polarizer)
In the polarizer side of obtained circular polarizer, there is aluminium using above-mentioned optics transparent adhesive material laminating evaporation PET film (Toray Advanced Film Co., Ltd.s system, trade name：Metalumy TS#50), formation determination sample.It is logical Cross spectrophotometer (Japanese light splitting society system, trade name：V7200 the reflectance spectrum under the sample reflects at 5 °) is determined.Determine ripple A length of 380nm~780nm.
By the way that obtained reflectance spectrum is multiplied by into color matching function y (λ) and is integrated, reflecting brightness Y is calculated.Now, D65 light sources are envisioned for as the white light source of benchmark.Its result is illustrated in table 9.
[table 10]
Table 9
It can be seen from the result of table 9, the reflecting brightness of the circular polarizer obtained in embodiment 110~112 is than comparative example 3 Reflecting brightness it is low, be excellent circular polarizer.

Claims (5)

1. a kind of hydrazine compound, represented by following formula (3), its be following formulas (E), (M), (Q), (S), (Y), (Z), (E1)、(G1)、(L1)、(O1)、(P1)、(Y1)、(Z1)、(A2)、(B2)、(C2)、(D2)、(E2)、(F2)、(I2)、(J2)、 (R2), any one in (S2) and (T2),
2. a kind of manufacture method of polymerizable compound, the polymerizable compound is represented that its feature exists by following formula (I)s In, carbonyls of the hydrazine compound with being represented by following formula (4) described in claim 1 is reacted,
In formula (4),
Y1~Y8Independently of one another represent chemical single bond ,-O- ,-S- ,-O-C (=O)-,-C (=O)-O- ,-O-C (=O)-O- ,- NR1- C (=O)-,-C (=O)-NR1- ,-O-C (=O)-NR1-、-NR1- C (=O)-O- ,-NR1- C (=O)-NR1-、-O-NR1- Or-NR1- O-, herein, R1Expression hydrogen atom or the alkyl that carbon number is 1~6,
G1、G2Represent there can be the divalence chain linear aliphatic base that the carbon number of substituent is 1~20 independently of one another, in above-mentioned chain In shape aliphatic group, can be inserted into have-O- ,-S- ,-O-C (=O)-,-C (=O)-O- ,-O-C (=O)-O- ,-NR2- C (=O)-,-C (=O)-NR2-、-NR2- or-C (=O)-, still ,-the O- or-S- for excluding more than 2 are each adjacent to situation about inserting, this Place, R2Expression hydrogen atom or the alkyl that carbon number is 1~6,
Z1、Z2The alkenyl that the carbon number that can be replaced with halogen atom is 2~10 is represented independently of one another,
A1Represent there can be the trivalent aromatic group of substituent,
A2、A3Represent there can be the divalence alicyclic type hydrocarbon that the carbon number of substituent is 3~30 independently of one another,
A4、A5Represent there can be the divalent aromatic radical that the carbon number of substituent is 6~30 independently of one another,
Q1Represent hydrogen atom or there can be the alkyl that the carbon number of substituent is 1~6,
In formula (I),
For Ax、Ay,
Work as AxForWhen, AyFor-CH2CH2CH2CH2CH2CH3,
Work as AxForWhen, AyFor hydrogen atom,
Work as AxForWhen, AyForC7H15-、CH3CH2CH2CH2OCH2CH2-、- CH2CH=CH2、 CF3CF2CF2CF2CH2CH2-、HC≡C-CH2-、HC≡C-CH2CH2-、CH3C≡CCH2-、CH3CH2C≡ CCH2CH2CH2CH2CH2CH2- or,
Y1~Y8、G1、G2、Z1、Z2、A1、A2、A3、A4、A5、Q1Each represent and identical implication in above-mentioned formula (4).
3. the manufacture method of polymerizable compound according to claim 2, wherein, make the hydrazine compound and the carbonyl Compound is reacted by 1: 2~2: 1 ratio of molar ratio computing.
4. the method that the manufacture raw material of a kind of hydrazine compound using described in claim 1 as polymerizable compound is used.
5. method according to claim 4, wherein, the polymerizable compound is liquid crystal compounds.
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